Stereoselective Palladium Catalyzed Synthesis of Indolines via Intramolecular Trapping of N-Ylides with Alkenes

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1 Supporting Information Stereoselective Palladium Catalyzed Synthesis of Indolines via Intramolecular Trapping of N-Ylides with Alkenes Angula Chandra Shekar Reddy, Venkata Surya Kumar Choutipalli, Jayanta Ghorai, Venkatesan Subramanian, and Pazhamalai Anbarasan* Department of Chemistry, Indian Institute of Technology Madras, Chennai , India. Chemical Laboratory, CSIR-Central Leather Research Institute, Chennai , India. Corresponding author s anbarasansp@iitm.ac.in Table of contents 1. General Comments 3 2. Analytical Methods 3 3. Synthesis of carbamate (1c) 4 4. Synthesis of amide (1d) 5 5. Synthesis of sulfonamide (1e) 6 6. Synthesis of N-Substituted 2-vinyl anilines (1) 7 7. Properties of N-Substituted 2-vinyl anilines (1) 7 8. Synthesis of N- Benzyl-2-(1-(thiophen-2-yl)vinyl)aniline (1ai) Typical procedure for the synthesis of aliphatic alkene substrates (1ak-1am) Synthesis of N-benzyl-2-(pro-1-en-2yl)aniline (1an) Synthesis of N-benzyl-2-vinylaniline (1ao) Synthesis of N-benzyl-2-(hexa-2,5-dien-2yl)aniline (1aq) Synthesis of N- benzyl-2-(cyclohexylidenemethyl)aniline (1as) Synthesis of 4-(Benzyloxy)-N-(4- methylbenzyl)-2-(1-phenylvinyl)aniline (1j) 34 1

2 15. Synthesis of 4-((tert-Butyldimethylsilyl)oxy)-N-(4-methylbenzyl)-2-(1-enylvinyl)aniline (1k) Synthesis of 4-((4-Methylbenzyl)amino)-3-(1-enylvinyl)phenyl acetate (1n) Synthesis of 4-((4-methylbenzyl)amino)-3-(1-phenylvinyl)phenyl 4-methylbenzenesulfonate (1o) Synthesis of methyl 2-((4-methoxy-2-(1-phenylvinyl)phenyl)(4-methylbenzylamino)-2- phenylacetate (4b) ptimization Typical procedure for the synthesis of substituted indolines (3) Properties of isolated indolines (3) Deuterium exchange experiment HPLC spectra for compound (3b) Crystallographic data and structure refinements summary for compound (3m) Crystallographic data and structure refinements summary for compound (3aq) Computational results References NMR spectras of isolated compounds 104 2

3 1. General Comments: All reactions were carried out under an atmosphere of dry Argon using reaction tubes. Dry toluene was prepared by distilling over sodium ketyl and stored over molecular sieves 4Å under argon atmosphere. All the α-diazo compounds were synthesized from corresponding esters and tosylazide employing literature procedure. 1 Similarly, all the 2-(α-arylvinyl)anilines were achieved from anilines and arylacetylenes, unless otherwise mentioned separately. 2 [Pd(Cinnamyl)Cl] 2 was prepared from known literature. 3 Column chromatography was performed using Rankem Silica gel ( mesh) and the solvent system used unless otherwise specified, was ethyl acetate-hexanes with various percentage of polarity depending on the nature of the substrate. Caution: Diazo compounds can decompose violently with the loss of N 2. Although no problems were faced in the present study due to the slow introduction of diazo compounds, the appropriate precautions should be taken. 2. Analytical Methods: NMR data were recorded on 400 and 500 MHz spectrometers. 13 C and 1 H NMR spectra were referenced to signals of deutero solvents and residual protiated solvents, respectively. Infrared spectra were recorded on a Thermo Nicolet is10 FT spectormeter. HRMS were recorded by electron spry ionization (ESI) method on a Q-TF Micro with lock spray source. Melting points are corrected. The crystal data were collected and integrated using a Bruker Axs kappa apex2 CCD diffractometer, with graphite monochromated Mo-K radiation. 3

4 3. Synthesis of carbamate (1c) 2-Vinyl aniline (550 mg, 2.44 mmol, 1 equiv), ethyl chloroformate (0.2 ml, 2.44 mmol, 1 equiv) and CHCl 3 (10 ml) were added under nitrogen atmosphere to an oven-dried 25ml round bottom flask equipped with stir bar. Solution was cooled to 0 ºC followed by 4M aq. solution of NaH (2.44 mmol, 1 equiv, 1.6 ml) was added. The reaction mixture was allowed towarmup to room temperature and stirredfor 2 h. After completion of reaction, the reaction mixture was dilute with EtAc, neutralized with NH 4 Cl and wash with brine. Evaporation of the organic layer followed by purification of the crude product through column chromatography using hexane/ethyl acetate mixture as eluent afforded 1c in 75% of yield as semi solid. R f = 0.47 in 2:8 EtAc/Hexane FTIR (Neat): 3420, 3055, 2984, 1727, 1608, 1520, 1266, 1209, 1036, 739 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.74 (s, 1H), (m, 5H), 6.81 (d, 1H, J = 8.9 Hz), 6.67 (s, 1H), 6.20 (s, 1H), 5.78 (s, 1H), 5.23 (s, 1H), 3.95 (q, 2H, J = 6.9 Hz), 3.68 (s, 3H), 1.06 (t, 3H, J = 6.9 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 155.9, 154.0, 146.1, 139.1, 128.7, 128.6, 128.4, 126.5, 122.6, 116.8, 115.6, 113.8, 61.0, 55.5, HRMS: calcd. for C 18 H 19 N 3 +Na: ; found:

5 4. Synthesis of amide (1d): In an oven dried 25 ml round bottom flask equipped with stir bar, 2-vinyl aniline (400 mg, 2.05 mmol, 1 equiv), trifluoroacetic anhydride (0.43 ml, 3.07 mmol, 1.5 equiv) were dissolved in pyridine (10 ml) under nitrogen atmosphere. The flask was kept at 120 C in pre-heated oil both. After completion of reaction, the reaction mixture was dilute with EtAc, neutralized with NH 4 Cl and wash with brine solution. Evaporation of the organic layer followed by purification of the crude product through column chromatography using hexane/ethyl acetate mixture as eluent afforded amide1d in 69% of yield as liquid. R f = 0.55 in 2:8 EtAc/Hexane FTIR (Neat): 3432, 3048, 1619, 1495, 1267, 1038, 906 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.95 (d, 1H, J = 8.8 Hz), 7.64 (s, 1H), (m, 5H), 6.93 (dd, 1H, J = 2.9, 8.8 Hz), (m, 1H), 5.85 (s, 1H), 5.38 (s, 1H), 3.81 (s, 3H) 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 157.8, (q, J = 36.9 Hz), 145.8, 138.7, 135.4, 129.0, 128.9, 128.6, 126.5, 125.5, 123.9, 117.8, 116.3, 113.8, 55.6 HRMS: calcd. for C 17 H 14 F 3 N 2 +H: ; found:

6 5. Synthesis of sulfonamide (1e): 2-Vinyl aniline (360 mg, 1.84 mmol, 1 equiv), tosyl chloride (526 mg, 2.76 mmol, 1.5 equiv.) were dissolved in pyridine (5 ml) under nitrogen atmosphere in an oven dried 25 mlround bottom flask equipped with stir bar. The flask was kept at 120 C in pre-heated oil both. After completion of reaction, the reaction mixture was dilute with EtAc, neutralized with NH 4 Cl and wash with brine solution. Evaporation of the organic layer followed by purification of the crude product through column chromatography using hexane/ethyl acetate mixture as eluent afforded sulfonamide 1e in 82% of yield as semi solid. R f = 0.32 in 2:8 EtAc/Hexane FTIR (Neat): 3345, 3058, 2987, 1596, 1482, 1266, 1163, 740 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.52 (d, 1H, J = 8.9 Hz), 7.30 (d, 2H, J = 7.9 Hz), (m, 3H), 7.01 (d, 2H, J = 8.0 Hz), 6.90 (s, 2H, J = 7.8 Hz), 6.79 (dd, 1H, J = 2.7, 8.8 Hz), 6.53 (d, 1H, J = 2.7 Hz), 6.08 (s, 1H), 5.42 (s, 1H), 4.61 (s, 1H), 3.65 (s, 3H), 2.27 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 157.2, 145.0, 143.5, 138.5, 136.1(6), 136.1(1), 129.4, 128.9, 128.5, 127.3, 126.9, 126.3, 125.0, 116.8, 115.8, 114.0, 55.4, HRMS: calcd. for C 22 H 21 N 3 S+Na: ; found:

7 6. Synthesis of N-Substituted 2-vinyl anilines (1): Substituted 2-vinyl anilines A (0.91 mmol, 1 equiv), carbonyl compound B (1.09 mmol, 1.2 equiv) and methanol (10 ml) were added under nitrogen atmosphere to an oven dried 25 ml round bottom flask equipped with stir bar. Subsequently, ZnCl 2 (1.09 mmol, 1.2 equiv) was added. The reaction tube was sealed with rubber septum and stirred for 1 h at room temperature. Next, the reaction mixture was cooled to 0 C followed by NaCNBH 3 (1.09 mmol, 1.2 equiv) was added portion wise. After completion of the reaction, the reaction mixture was dilute with EtAc, neutralized with NH 4 Cl and wash with brine solution. Evaporation of the organic layer followed by purification of the crude product through column chromatography using hexane/ethyl acetate mixture as eluent afforded N-substituted 2-vinyl anilines 5 in high yield and purity. 7. Properties of N-Substituted 2-vinyl anilines (1): 4-Methoxy-N-(4-methylbenzyl)-2-(1-phenylvinyl)aniline (1b): According to the general procedure the product was isolated in 86% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. 7

8 R f = 0.70 in 1:9 EtAc/Hexane FTIR (Neat): 3422, 2932, 1688, 1514, 1247, 90, 733 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 2H), (m, 2H), (m, 2H), 6.48 (d, 1H, J = 8.4 Hz), 5.68 (s, 1H), 5.25 (s, 1H), 4.01 (s, 2H), 3.62 (s, 3H), 3.62 (s, 1H), 2.18 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.6, 147.1, 139.8, 139.6, 136.6, 136.5, 129.2, 128.8, 128.6, 128.2, 127.2, 126.7, 116.8, 116.5, 114.1, 112.3, 55.9, 48.7, 21.1 HRMS: calcd. for C 23 H 23 N+H: ; found: N-(4-Methylbenzyl)-2-(1-phenylvinyl)aniline (1f): According to the procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.80 in 1:9 EtAc/Hexane FTIR (Neat): 3425, 3057, 2848, 1602, 1504, 1451, 1360, 1317, 908, 741 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 4.34 (d, 2H, J = 7.8 Hz), 4.23 (s, 1H), 2.47 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.3, 145.4, 139.9, 136.5, 136.3, 130.6, 129.2, 129.0, 128.6, 128.1, 127.3, 127.1, 126.7, 116.9, 116.4, 110.8, 47.8,

9 HRMS: calcd. for C 22 H 21 N+H: ; found: Methyl-N-(4-methylbenzyl)-2-(1-phenylvinyl)aniline (1g): According to the procedure the product was isolated in 76% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.79 in 1:9 EtAc/Hexane FTIR (Neat): 3422, 3023, 2922, 1685, 1614, 1504, 1304, 1181, 1027, 897 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 3H), (m, 3H), (m, 3H), 6.58 (d, 1H, J = 8.2 Hz), 5.80 (d, 1H, J = 1.4 Hz), 5.38 (d, 1H, J = 1.3 Hz), 4.18 (s, 2H), 3.93 (s, 1H), 2.32 (s, 3H), 2.28 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.4, 143.2, 140.0, 136.6, 136.5, 131.2, 129.4, 129.2, 128.6, 128.1, 127.6, 127.1, 126.8, 126.0, 116.2, 111.1, 48.2, 21.1, HRMS: calcd. for C 23 H 23 N+H: ; found: (tert-Butyl)-N-(4-methylbenzyl)-2-(1-phenylvinyl)aniline (1h): 9

10 According to the procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.80 in 1:9 EtAc/Hexane FTIR (Neat): 3433, 3054, 2961, 1677, 1605, 1267, 910 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 5H), 7.28 (d, 2H, J = 7.6 Hz), 7.19 (d, 2H, J = 7.2 Hz), 6.86 (dd, 1H, J = 1.0, 8.4 Hz), 6.05 (s, 1H), 5.66 (s, 1H), 4.40 (s, 2H), 4.18 (s, 1H), 2.54 (s, 3H), 1.58 (s, 9H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.7, 143.1, 139.9, 139.5, 136.6, 136.4, 129.1, 128.5, 128.0, 127.6, 127.1, 127.0, 126.7, 125.6, 116.1, 110.4, 48.0, 33.8, 31.7, HRMS: calcd. for C 26 H 29 N+H: ; found: N-(4-methylbenzyl)-3-(1-phenylvinyl)-[1, 1 -biphenyl]-4-amine (1i): According to the procedure the product was isolated in 62% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.78 in 1:9 EtAc/Hexane FTIR (Neat): 3424, 3028, 2856, 1696, 1606, 1517, 1406, 1313, 1267, 1171, 1081, 905, 810 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), 7.46 (dd, 1H, J = 1.5, 8.4 Hz), (m, 3H), (m, 2H), (m, 3H), (m, 1H), (m, 2H),

11 6.88 (m, 2H), 6.68 (d, 1H, J = 8.4 Hz), 5.83 (s, 1H), 5.43 (S, 1H), 4.21 (s, 2H), 4.12 (S, 1H), 2.20 (S, 3H) 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.2, 144.8, 141.1, 139.7, 136.7, 136.2, 129.7, 129.3, 129.2, 128.7, 128.7(3), 128.3, 127.6, 127.5, 127.1, 126.8, 126.3, 126.1, 116.7, 111.1, 47.8, HRMS: calcd. for C 28 H 25 N+H: ; found: N-(4-Methylbenzyl)-6-(1-phenylvinyl)benzo[1,3]dioxol-5-amine (1l): According to the procedure the product was isolated in 65% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. R f = 0.46 in 1:9 EtAc/Hexane FTIR (Neat): 3425, 3025, 2883, 1617, 1491, 1348, 1191, 1034, 924, 864 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), 7.03 (d, 2H, J = 7.8 Hz), 6.90 (d, 2H, J = 7.9 Hz), 6.66 (s, 1H), 6.30 (s, 1H), 5.87 (s, 2H), 5.75 (d, 1H, J = 1.4 Hz), 5.34 (d, 1H, J = 1.4 Hz), 4.10 (s, 2H), 3.89 (s, 1H), 2.30 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 148.2, 147.1, 141.2, 140.2, 138.9, 136.6, 136.3, 129.2, 128.6, 128.2, 127.2, 126.8, 119.5, 116.6, 110.9, 100.7, 94.3, 48.8, HRMS: calcd. for C 23 H 21 N 2 +H: ; found:

12 4-Fluoro-N-(4-methylbenzyl)-6-(1-phenylvinyl)aniline (1m): According to the procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.79 in 1:9 EtAc/Hexane FTIR (Neat): 3456, 3084, 1607, 1493, 1269, 909 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), 7.00 (d, 2H, J = 7.7 Hz), (m, 4H), (m, 2H), 5.76 (d, 1H, J = 0.8 Hz), 5.33 (d, 1H, J = 0.9 Hz), 4.09 (s, 2H), 3.86 (s, 1H), 2.26 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 156.5, 154.2, 146.4, 141.8, 139.2, 136.6, 136.1, 129.2, 128.7, 128.4, 127.1, 126.7, (d, J = 22.5 Hz), 116.9, (d, J = 21.6 Hz), (d, J = 7.4 Hz), 48.4, HRMS: calcd. for C 22 H 20 NF+H: ; found: Ethyl 4-(benzylamino)-3-(1-enylvinyl) benzoate (1p): According to the general procedure the product was isolated in 38% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. R f = 0.53 in 1:9 EtAc/Hexane 12

13 FTIR (Neat): 3426, 3056, 2984, 1698, 1604, 1521, 1263, 1129, 913 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.90 (dd, 1H, J = 1.7, 8.6 Hz), 7.84 (d, 1H, J = 1.9 Hz), (m, 5H), (m, 3H), (m, 2H), 6.56 (d, 1H, J = 8.6 Hz), 5.83 (d, 1H, J = 1.2 Hz), 5.41 (d, 1H, J = 1.2 Hz), 4.46 (t, 1H, J = 5.2 Hz), 4.30 (q, 2H, J = 7.0 Hz), 4.25 (d, 2H, J = 5.6 Hz), 1.34 (t, 3H, J = 7.1 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 167.0, 148.9, 146.3, 139.1, 138.4, 132.2, 131.4, 128.8, 128.6, 128.4, 127.3, 127.0, 126.6, 126.5, 118.6, 117.3, 109.5, 60.3, 47.5, HRMS: calcd. for C 24 H 23 N 2 +H: ; found: ,5-Dimethyl-N-(4- methylbenzyl)-2-(1-phenylvinyl)aniline (1q): According to the procedure the product was isolated in 83% yield using the mixture of ethyl acetate/hexanes (0:100) as an eluent for column chromatography. R f = 0.80 in 1:9 EtAc/Hexane FTIR (Neat): 3423, 3020, 2922, 1588, 1445, 1322, 1177, 1114, 912 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 4H), 6.50 (s, 1H), 6.41 (s, 1H), 6.05 (s, 1H), 5.03 (s, 1H), 4.25 (s, 2H), 4.25 (s, 1H), 2.33 (s, 3H), 2.31 (s, 3H), 2.08 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 145.5, 145.0, 139.3, 137.8, 136.7, 136.5, 129.2, 128.6, 128.0, 127.2, 126.1, 124.3, 119.6, 116.8, 109.0, 48.0, 21.8, 21.1,

14 HRMS: calcd. for C 24 H 25 N+H: ; found: N-(4-methybenzyl)-2-(1-phenylvinyl)-4-styrylaniline (1r): According to the procedure the product was isolated in 58% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.77 in 1:9 EtAc/Hexane FTIR (Neat): 3423, 3023, 2923, 2857, 1599, 1453, 1418, 1317, 1191, 1077, 906, 802 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 9H), (m, 1H), (m, 3H), (m, 3H), 6.59 (d, 1H, J = 8.3 Hz), 5.82 (s, 1H), 5.40 (s, 1H), 4.18 (s, 2H), 4.15 (s, 1H), 2.28 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.0, 145.1, 139.5, 138.2, 136.7, 136.0, 129.2, 128.8, 128.7, (0), 128.3, 127.7, 127.5, 127.0, 126.8, 126.7, 126.3, 126.1, 124.7, 116.7, 110.9, 47.7, HRMS: calcd. for C 30 H 27 N+H: ; found:

15 4-((4-Methylbenzyl)amino)-3-(1-phenylvinyl)phenol (1s): According to the procedure the product was isolated in 58% yield using the mixture of ethyl acetate/hexanes (10:90) as an eluent for column chromatography. R f = 0.43 in 2:8 EtAc/Hexane FTIR (Neat): 3394, 3022, 2920, 1614, 1508, 1447, 1309, 1213, 1026, 907 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), 7.03 (d, 2H, J = 7.7 Hz), 6.91 (d, 2H, J = 7.7 Hz), (m, 2H), 6.57 (d, 1H, J = 8.5 Hz), 5.77 (s, 1H), 5.33 (s, 1H), 4.12 (s, 2H), 2.31 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.4, 146.8, 139.7, 139.6, 136.6, 136.4, 129.2, 129.1, 128.6, 128.2, 127.3, 126.7, 117.9, 116.5, 115.7, 112.9, 49.0, HRMS: calcd. for C 22 H 21 N+H: ; found: N-Benzyl-4-methoxy-2-(1-phenylvinyl)aniline (1u): According to the procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.71 in 1:9 EtAc/Hexane 15

16 FTIR (Neat): 3440, 2925, 1602, 1386, 1104, 908 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 3H), (m, 3H), (m, 2H), (m, 2H), (m, 1H), 5.79 (s, 1H), 5.38 (s, 1H), 4.14 (d, 2H), 3.72 (s, 3H), 3.71(s, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.6, 147.1, 139.6(9), 139.6(3), 128.7, 128.6, 128.4, 128.2, 127.2, 126.9, 126.7, 116.8, 116.5, 114.1, 112.2, 55.8, HRMS: calcd. for C 22 H 21 N+H: ; found: Methoxy-N-(4-methoxybenzyl)-2-(1-phenylvinyl)aniline (1v): According to the procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. R f = 0.51 in 1:9 EtAc/Hexane FTIR (Neat): 3425, 3065, 2926, 1606, 1502, 1452, 1298, 1249, 1170, 1031, 902 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), 6.96 (d, 2H, J = 7.8 Hz), (m, 1H), (m, 3H), 6.63 (d, 1H, J = 8.6 Hz), 5.81 (s, 1H), 5.38 (s, 1H), 4.11 (s, 2H), 3.78 (s, 3H), 3.77 (s, 3H), 3.72 (s, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 158.6, 151.6, 147.1, 139.8, 139.7, 131.7, 128.8, 128.6, 128.4, 128.2, 126.7, 116.8, 116.5, 114.1, 113.9, 112.4, 55.9, 55.3, HRMS: calcd. for C 23 H 23 N 2 +H: ; found:

17 N-(Furan-2-ylmethyl)-4-methoxy-2-(1-phenylvinyl)aniline (1x): According to the procedure the product was isolated in 73% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. R f = 0.66 in 1:9 EtAc/Hexane FTIR (Neat): 3403, 2929, 1678, 1607, 1502, 1288, 1220, 1038, 910 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 6H), 6.82 (dd, 1H, J = 3.0, 8.8 Hz), (m, 2H), 6.21 (dd, 1H, J = 1.9, 3.1 Hz), (m, 1H), 5.81 (s, 1H), 5.32 (s, 1H), 4.16 (s, 2H), 3.80 (s, 1H), 3.74 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 153.3, 152.0, 146.9, 141.6, 139.6, 139.3, 129.4, 128.6, 128.2, 128.7, 116.7, 116.5, 114.2, 113.0, 110.2, 106.5, 55.9, HRMS: calcd. for C 20 H 19 N 2 +H: ; found: Methoxy-N-(1-phenylethyl)-2-(1-phenylvinyl)aniline (1y): According to the procedure the product was isolated in 47% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. 17

18 R f = 0.80 in 1:9 EtAc/Hexane FTIR (Neat): 3429, 3056, 2959, 1604, 1506, 1436, 1228, 1018, 736 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 2H), (m, 1H), (m, 2H), 6.66 (d, 1H, J = 2.9 Hz), 6.57 (dd, 1H, J = 2.9, 8.7 Hz), 6.25 (d, 1H, J = 8.8 Hz), 5.72 (s, 1H), 5.31 (s, 1H), 4.20 (q, 1H, J = 6.6 Hz), 3.61 (s, 3H), 3.61 (s, 1H), 1.08 (d, 3H, J = 6.7 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.3, 147.4, 145.7, 139.9, 139.0, 128.6, 128.5(9), 128.5(6), 128.3, 126.9, 126.7, 125.9, 116.8, 116.6, 114.0, 113.0, 55.8, 54.1, HRMS: calcd. for C 23 H 23 N+H: ; found: N-Isopropyl-4-methoxy-2-(1-phenylvinyl)aniline (1z): According to the procedure the product was isolated in 83% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.79 in 1:9 EtAc/Hexane FTIR (Neat): 3403, 2958, 1502, 1298, 1210, 1038, 903 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.84 (m, 1H), (m, 5H), (m, 1H), (m, 1H), 6.28 (s, 1H), 5.87 (s, 1H), 5.32 (s, 1H), (m, 2H), 3.78 (s, 3H), (m, 1H), (m, 1H), (m, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 146.1, 139.2, 128.7, 128.4, 126.6, 116.8, 115.6, 113.9, 61.0, 55.6, HRMS: calcd. for C 18 H 20 N+H: ; found:

19 N-Cyclopentyl-4-methoxy-2-(1-enylvinyl)aniline (1aa): According to the procedure the product was isolated in 70% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.78 in 1:9 EtAc/Hexane FTIR (Neat): 3408, 2943, 1596, 1498, 1288, 1215, 1040, 899 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 3H), 6.83 (dd, 1H, J = 3.0, 8.7 Hz), 6.74 (d, 1H, J = 3.0 Hz), 6.63 (d, 1H, J = 8.7 Hz), 5.74 (d, 1H, J = 1.5 Hz), 5.33 (d, 1H, J = 1.4 Hz), 3.76 (s, 3H), (m, 1H), 3.26 (s, 1H), (m, 2H), (m, 4H), (m. 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.2, 147.4, 139.9, 139.8, 128.7, 128.6, 128.2, 126.7, 116.8, 116.5, 114.3, 112.9, 55.9, 55.4, 33.3, HRMS: calcd. for C 20 H 23 N+H: ; found: N-Cyclohexyl-4-methoxy-2-(1-phenylvinyl)aniline (1ab): 19

20 According to the procedure the product was isolated in 82% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.73 in 1:9 EtAc/Hexane FTIR (Neat): 3406, 2919, 1598, 1500, 1281, 1227, 1044, 895 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 1H), 6.77 (m, 1H), (m, 1H), 5.80 (s, 1H), 5.37 (s, 1H), 3.78 (s, 3H), 3.26 (s, 1H), (m, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.1, 147.4, 139.9, 139.2, 128.8, 128.6, 128.1, 126.8, 116.7, 116.5, 114.4, 113.1, 55.9, 52.4, 33.1, 25.9, HRMS: calcd. for C 21 H 25 N+H: ; found: N-(4-Methoxy-2-(1-enylvinyl)phenyl)cycloheptanamine (1ac): According to the procedure the product was isolated in 64% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.71 in 1:9 EtAc/Hexane FTIR (Neat): 3415, 2918, 1598, 1502, 1285, 1216, 1042, 899 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), 6.82 (dd, 1H, J = 3.0, 8.7 Hz), 6.73 (d, 1H, J = 3.0 Hz), 6.55 (d, 1H, J = 8.8 Hz), 5.76 (d, 1H, J = 1.4 Hz), 5.33 (d, 1H, J = 1.4 Hz),

21 (s, 3H), (m, 1H), 3.28 (s, 1H), (m, 2H), (m, 2H), (m, 6H), (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.1, 147.4, 139.9, 139.2, 128.9, 128.6, 128.2, 126.8, 116.9, 116.5, 114.4, 112.9, 55.9, 54.2, 34.6, 28.4, HRMS: calcd. for C 22 H 27 N+H: ; found: Methoxy-N-(4-methylbenzyl)-2-(1-(p-tolyl)vinyl)aniline (1af): According to the procedure the product was isolated in 76% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.69 in 1:9 EtAc/Hexane FTIR (Neat): 3420, 2935, 2864, 1600, 1457, 1114 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), 5.64 (s, 1H), 5.19 (s, 1H), 4.01 (s, 2H), 3.65 (s, 1H), 3.62 (s, 3H), 2.24 (s, 3H), 2.18 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.5, 146.9, 139.8, 138.0, 136.7, 136.6, 136.4, 129.3, 129.1, 128.9, 127.2, 126.6, 116.7, 115.5, 114.0, 112.2, 55.8, 48.7, 21.2, HRMS: calcd. for. C 24 H 25 N+H: ; found:

22 2-(1-4-(tert-Butyl)phenylvinyl)-4-methoxy-N-(methylbenzyl)aniline (1ag): According to the procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.70 in 1:9 EtAc/Hexane FTIR (Neat): 3449, 2987, 2963, 2922, 1674, 1466, 1271, 909 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), 5.78 (s, 1H), 5.29 (s, 1H), 4.10 (s, 2H), 3.72 (s, 1H), 3.72 (s, 3H), 2.27 (s, 3H), 1.32 (s, 9H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.6, 151.3, 146.8, 139.8, 136.6, 136.6(3), 136.5, 129.1, 129.0, 127.3, 126.4, 125.5, 116.8, 115.6, 114.0, 112.3, 55.8, 48.8, 34.6, 31.4, HRMS: calcd. for. C 27 H 31 N+H: ; found:

23 2-(1-(4-Fluorophenyl)vinyl)-4-methoxy-N-(4-methylbenzyl)aniline (1ah): According to the procedure the product was isolated in 68% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.69 in 1:9 EtAc/Hexane FTIR (Neat): 3435, 2963, 1609, 1511, 1229, 1112, 908 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 4H), (m, 2H), (m, 1H), 5.86 (s, 1H), 5.48 (s, 1H), 4.27 (s, 2H), 3.87 (s, 1H), 3.86 (s, 3H), 2.44 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ (J = Hz), 151.5, 146.0, 139.6, (J = 3.5 Hz), 135.7, 129.1, 128.4, 128.3, 127.1, 116.7, 116.1, 115.4, 115.2, 114.1, 112.2, 55.6, 48.6, HRMS: calcd. for C 23 H 22 FN+H: ; found:

24 2-(1-(Cyclohex-1-en-1-yl)vinyl)-4-methoxy-N-(4-methylbenzyl)aniline (1aj): According to the procedure the product was isolated in 31% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.68 in 1:9 EtAc/Hexane FTIR (Neat): 3424, 3064, 2864, 2368, 2075, 1950, 1805, 1609, 1503, 1449, 1369, 1048 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), 6.72 (dd, 1H, J = 3.0, 8.7 Hz), 6.61 (d, 1H, J = 3.0 Hz), 6.56 (d, 1H, J = 8.7 Hz), 5.6 (t, 1H, J = 4.0 Hz), 5.35 (s, 1H), 4.99 (s, 1H), 4.22 (s, 2H), 3.86 (s, 1H), 3.72 (s, 3H), 2.31 (s, 3H), (m, 2H), (m, 2H), (m, 2H), (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 151.4, 148.3, 139.8, 137.0, 136.6, 135.3, 129.5, 129.2, 129.1, 127.3, 116.6, 113.3, 112.8, 111.9, 55.8, 48.9, 26.0, 25.5, 22.9, 22.2, HRMS: calcd. for C 23 H 27 N+H: ; found:

25 8. Synthesis of N-benzyl-2-(1-(thiophen-2-yl)vinyl)aniline (1ai): Step-I: In a 25 ml double neck RB flask, Mg (85 mg, 3.55 mmol) was weighed under argon atmosphere. ne of the neck was connected with a condenser another one was with vacuum adaptor which was connected to high vacuum. The condenser was closed with rubber septum and heated with hot gun to activate the Mg metal. The flask was cooled down to room temperature under argon atmosphere and catalytic amount of I 2 dissolve in THF (2 ml) was added. Next, THF (10 ml) solution of 2-bromo thiophene (3.11 mmol) was introduced slowly and the mixture was allowed stir for 20 min. Finally, clear grey color solution of Grignard reagent was formed after all Mg was consumed. Consequently, THF (5 ml) solution of N-benzyl 2-amino acetophenone (200 mg, 0.88 mmol) was slowly introduced through syringe to Grignard reagent obtained above. The reaction mixture was allowed to stir for 6 h. After completion of the reaction, saturated NH 4 Cl was added and extracted with EtAc. Finally, the product was isolated in 51% yield using the mixture of ethyl acetate/hexanes (4:96) as an eluent for column chromatography. 25

26 Step II: In a dried 50 ml RB flask, 1-(2-(benzylamino)phenyl)-1-(thiophen-2yl)ethanol (130 mg, 0.40 mmol ) and p-tsa (3.8 mg, 0.02 mmol) were dissolved in dry toluene (4 ml) and reflux for 1h. After completion of the reaction, water was added and extract with EtAc. The product was isolated in 91% yieldusing the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.77 in 1:9 EtAc/Hexane FTIR (Neat): 3456, 3153, 2924, 2369, 2271, 2055, 1649, 1502, 1438, 1315, 1119, 893cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 8H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 5.79 (s, 1H), 5.2 (s, 1H), 4.28 (s, 1H), 4.28 (s, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 145.3, 144.4, 140.7, 139.5, 130.1, 129.2, 128.6, (6), (1), 126.7, 126.3, 125.5, 116.8, 114.9, 110.9, HRMS: calcd. for C 19 H 17 NS+H: ; found: Typical procedure for synthesis of aliphatic alkene substrates (1ak-1am): Step-I: In a 50 ml double neck RB flask, Mg (10.09 mmol, 4.2 eqiuv) was weighed under argon atmosphere. ne of the neck was connected with a condenser another one was with vacuum adaptor which was connected to high vacuum. The condenser was closed with rubber septum and 26

27 heated with hot gun to activate the Mg metal. The flask was cooled down to room temperature under argon atmosphere and catalytic amount of I 2 dissolve in THF (2 ml) was added. Next, THF (10 ml) solution of R-Br (9.25 mmol, 3.85 equiv) was introduced slowly and the mixture was allowed stir for 30 min. Finally, clear grey color solution of Grignard reagent was formed after all Mg was consumed. Consequently, THF (10 ml) solution of 2-(benzylamino)benzonitrile (2.40 mmol, 1 equiv) was slowly introduced through syringe to Grignard reagent obtained above. The reaction mixture was allowed to stir for 6 h. After completion of the reaction, saturated NH 4 Cl was added and extracted with EtAc. Finally, the product was isolated by using the mixture of ethyl acetate/hexanes as an eluent for column chromatography. Step-II: In an oven dried 50 ml round bottom flask, CH 3 P 3 Br (1.63 mmol, 2.5 equiv) was weighed in argon atmosphere and dried under vacuum at 50 C for 20 min. The salt was cooled to room temperature and dissolved in THF. The THF solution was cooled to 0 C and n BuLi (1.95 mmol, 3 equiv) was introduced through syringe. Next, amino ketone (0.65 mmol, 1 equiv) was added slowly and allows to stirr vigorously for 3h at room temperature. After completion of the reaction, saturated NH 4 Cl solution was added and extracted with EtAc. Removal of solvent under reduced pressure followed by purification using the mixture of ethyl acetate/hexanes as an eluent for column chromatography. 27

28 N-Benzyl-2-(5-methylhex-1-en-2yl)aniline (1ak): According to the procedure the product was isolated in 41% yield using hexanes as an eluent for column chromatography. R f = 0.81 in 1:9 EtAc/Hexane FTIR (Neat): 3432, 2924, 2858, 2368, 1732, 1631, 1504, 1453, 1270, 1028, 909 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 5.25 (s, 1H), 5.05 (s, 1H), 4.47 (s, 1H), 4.33 (s, 2H), 2.44 (s, 2H), (m, 1H), (m, 2H), (m, 6H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 148.4, 144.6, 139.7, 129.0, 128.7, 128.2, 128.1, 127.3, 127.1, 116.7, 114.7, 110.5, 48.2, 37.3, 35.53, 27.96, HRMS: calcd. for C 20 H 25 N+H: ; found: N-Benzyl-2-(hex-1-en-2yl)aniline (1al): According to the procedure the product was isolated in 51% yield using hexanes as an eluent for column chromatography. R f = 0.81 in 1:9 EtAc/Hexane FTIR (Neat): 3432, 3060, 2929, 2862, 2374, 1590, 1449, 1299, 1043, 907 cm 1. 28

29 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 1H), 6.95 (dd, 1H, J = 1.5, 7.4 Hz), 6.67 (td, 1H, J = 1.1, 7.4 Hz), 6.59 (d, 1H, J = 8.1 Hz), (m, 1H), 5.05 (d, 1H, J = 2.1 Hz), 4.48 (s, 1H), 4.34 (d, 2H, J = 4.5 Hz), 2.35 (t, 2H, J = 7.7 Hz), (m, 4H), 0.88 (t, 3H, J = 7.1 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 133.7, 128.7, 128.3, 128.1, 127.3, 127.2, 116.7, 114.9, 110.6, 48.3, 37.4, 30.3, 22.6, HRMS: calcd. for C 19 H 23 N+H: ; found: N-Benzyl-2-(oct-1-en-2yl)aniline (1am): According to the procedure the product was isolated in 68% yield using hexanes as an eluent for column chromatography R f = 0.81 in 1:9 EtAc/Hexane FTIR (Neat): 3507, 3056, 2929, 2612, 2362, 1801, 1736, 1627, 1505, 1451, 1060, 904 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), 7.15 (m, 1H), 7.02 (m, 1H), 6.68 (td, 1H, J = 1.1, 7.4 Hz), 6.59 (d, 1H, J = 8.0 Hz), 5.25 (s, 1H), 5.05 (s, 1H), 4.48 (s, 1H), 4.33 (s, 2H), 2.35 (t, 2H, J = 6.9 Hz), (m, 2H), (m, 6H), 0.86 (t, 3H, J = 5.1 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 148.2, 144.6, 139.7, 129.0, 128.7, 128.3, 128.1, 127.3, 127.2, 116.7, 114.9, 110.5, 48.3, 37.7, 31.8, 29.2, 28.1, 22.7, HRMS: calcd. for C 21 H 27 N+H: ; found:

30 10. Synthesis of N-benzyl-2-(pro-1-en-2yl)aniline (1an): In an oven dried 50 ml round bottom flask, CH 3 P 3 Br (2.37 gm, 6.66 mmol, 3 equiv) was weighed in argon atmosphere and dried under vacuum at 50 C for 20 min. The salt was cooled to room temperature and dissolved in THF. The THF solution was cooled to 0 C and n BuLi (3 equiv) was introduced through syringe. Next, N-benzyl 2-aminoacetophenone (500 mg, 2.22 mmol, 1equiv) was added slowly and allowed to stirr vigorously for 3h at room temperature. After completion of the reaction, saturated NH 4 Cl solution was added and extracted with EtAc. Removal of solvent under reduced pressure followed by purification using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography yielded the product 1an in 76% yield. R f = 0.81 in 1:9 EtAc/Hexane FTIR (Neat): 3432, 2951, 1599, 1401, 1117 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 5.26 (m, 1H), 5.06 (m, 1H), 4.50 (s, 1H), 4.30 (d, 2H, J = 1.4 Hz), 2.05 (m, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 144.3, 143.7, 139.7, 129.5, 128.8, 128.3, 128.0, 127.4, 127.2, 117.0, 115.9, 110.8, 48.4, HRMS: calcd. for C 16 H 19 N+H: ; found:

31 11. Synthesis of N-benzyl-2-vinyl aniline (1ao): In a ven dried reaction tube, 2-bromo styrene (1 equiv), Pd 2 (dba) 3, X-os, t-buk were dissolved in 1,4 Dioxane. To the reaction mixture benzyl amine (1.2 eq) was added and kept under pre-heated oil both at 110 C for 12 hr. After completion of reaction cool to room temperature and filter with celite, purified through the column chromatography by using (2:98 EtAc/Hexane) ratio with 68% of yield. R f = 0.51 in 0:10 EtAc/Hexane FTIR (KBr): 3416, 3076, 2951, 1599, 1345, 1401, 1117 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), (m, 2H), (m, 1H), (m, 2H), 6.66 (d, 1H, J = 8.1 Hz), 5.64 (dd, 1H, J = 1.3, 17.3 Hz), 5.32 (dd, 1H, J = 10.9, 1.3 Hz), 4.38 ( s, 2H), 4.18 (s, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 145.2, 139.4, 133.1, 129.1, 128.8, 127.6, 127.5, 127.4, 124.4, 117.7, 116.5, 111.1, HRMS: calcd. for C 15 H 15 N+H: ; found:

32 12. Synthesis of N-benzyl-2-(hexa-2,5-dien-2yl)aniline (1aq): Step-1: In a 100 ml double neck RB flask, Mg (268.4 mg, mmol) was weighed under argon atmosphere. ne of the neck was connected with a condenser another one was with vacuum adaptor which was connected to high vacuum. The condenser was closed with rubber septum and heated with hot gun to activate the Mg metal. The flask was cooled down to room temperature under argon atmosphere and catalytic amount of I 2 dissolve in THF (2 ml) was added. Next, THF (10 ml) solution of 4-bromobut-1-ene was introduced slowed and the mixture was allowed stir for 30 min. Finally, clear grey color solution of Grignard reagent was formed after all Mg was consumed. Consequently, THF (5 ml) solution of N-benzyl-2-aminoacetophenone (360 mg, 1.59 mmol) was slowly introduced through syringe to Grignard reagent obtained above. The reaction mixture was allowed to stir for 6 h. After completion of the reaction, saturated NH 4 Cl was added and extracted with EtAc. Finally, the product was isolated in 65% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. Step II: In a dried 50 ml RB flask, 2-(2-(benzylamino)phenyl)propan-2-ol (200 mg, 0.71 mmol ) and p-tsa (2.6 mg, mmol) were dissolved in dry toluene (4 ml) and reflux for 3h. 32

33 After completion of the reaction, water was added and extract with EtAc. The product was isolated in 94% yield (A: B = 1:0.38) using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. R f = 0.82 in 1:9 EtAc/Hexane FTIR (Neat): 3437, 2978, 2922, 1594, 1415, 1111, 911 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 8H), (m, 2H), (m, 2.4H), (m, 1.3H), (m, 0.64H), (m, 2H), (m, 2H), (m, 2H), (m, 0.61H), (m, 1H), (m, 0.38H), (m, 4.5H), (m, 6H), 2.91 (t, 2.2H, J = 6.3 Hz), (m, 1.2H), (0.7H), 2.34 (s, 0.2H), 2.25 (s, 0.2H), (m, 0.8H), 1.97 (s, 2H), 1.94 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.1, 144.7, 144.5, 144.2, 139.8, 139.7(6), 139.7(0), 138.3, 137.2, 136.5, 135.0, 134.9, 131.4, 128.7, 128.5, (9), 128.3(5), 128.2, 128.0, 127.9, 127.3, 127.1, 117.0, 116.7, 115.5, (9), (6), 114.6, 110.6, 110.3, 48.3(7), 48.3(2), 48.2, 36.8, 33.66, 32.65, 32.1, 24.8, HRMS: calcd.c 19 H 21 N+H: ; found: Synthesis of N-benzyl-2(cyclohexylidenemethyl)aniline (1as): In an oven dried reaction tube Pd 2 (dba) 3 (8.2 mg, 0.75 mol%), X-os (12.5 mg, 2.2 mol%), and K t Bu (267 mg, 2 equiv) was added under argon atmosphere. Subsequently, Bromo arene (300 mg, 1 equiv), benzyl amine (0.18 ml,1.2 equiv) and 1,4-dioxane were added, reaction tube was 33

34 sealed and kept at 110 C in pre-heated oil both. After completion of the reaction, it was diluted with EtAc and washed with brine solution. Evaporation of solvent followed by purification of the resultant crude through column chromatography using hexane/ethyl acetate with ratio (1:99), afforded coupled product 1as in 67 % yield. R f = 0.79 in 1:9 EtAc/Hexane FTIR (Neat): 3431, 3064, 2933, 1596, 1461, 1343, 1206, 1029 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 1H), 7.02 (m, 1H ), 6.70 (t, 1H, J = 7.3 Hz), 6.61 (d, 1H, J = 8.1 Hz), 6.02 (s, 1H), 4.39 (s, 2H), 4.22 (s, 1H), 2.30 (t, 2H, J = 5.2 Hz), 2.25 (m, 2H), (m, 6H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 146.0, 145.8, 139.8, 130.0, 128.7, 127.7, 127.4, 127.1, 123.8, 117.6, 116.7, 110.1, 48.3, 37.2, 30.1, 28.9, 28.1, HRMS: calcd. for C 20 H 23 N+Na: ; found: Synthesis of 4-(Benzyloxy)-N-(4- methylbenzyl)-2-(1-phenylvinyl)aniline (1j): 4-((4-Methylbenzyl)amino)-3-(1-phenylvinyl)phenol (300 mg, mmol, 1 equiv) was dissolved in mixture of CH 2 Cl 2 (10 ml) and 20% aq. NaH (2 ml). Subsequently, tetrabutyl ammonium bromide (230 mg, mmol, 1 equiv), benzyl bromide (0.13 ml, mmol, 1.2 equiv) were added and the reaction mixture was vigorously stirred at r.t for 1h. After completion 34

35 of the reaction, it was diluted with water and extracted with CH 2 Cl 2. The combined organic layer was dried over anhydrous Na 2 S 4, evaporated and purified through column chromatography using ethyl acetate and hexane (2:98) mixture to obtain the title compound (162 mg, 42% yield). R f = 0.67 in 1:9 EtAc/Hexane FTIR (Neat): 3426, 3050, 2864, 1609, 1506, 1267, 1025, 907 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 10H), (m, 2H), (m, 4H), (m, 1H), 5.75 (s, 1H), 5.33 (s, 1H), 4.95 (s, 2H), 4.09 (s, 2H), 3.74 (s, 1H), 2.26 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 150.7, 147.1, 140.1, 139.7, 137.6, 136.6, 136.5, 129.1, (8), (4), 128.5, 128.2, 127.8, 127.6, 127.1, 126.7, 118.1, 116.5, 115.4, 112.1, 70.9, 48.6, HRMS: calcd. for C 29 H 27 N+H: ; found: Synthesis of 4-((tert-butyldimethylsilyl)oxy)-N-(4-methylbenzyl)-2-(1- enylvinyl)aniline (1k): 1H-Imidazole (113 mg, 1.66 mmol, 1.5 equiv) was added to the solution of phenol (350 mg, 1.10 mmol, 1 equiv) and TBDMSCl (183 mg, 1.22 mmol, 1.1 equiv) in DMF (10 ml) at room temperature. The reaction mixture was allowed to stir for 3 h and it was diluted with CH 2 Cl 2 and 35

36 washed with brine solution. Evaporation of solvent followed by purification through column chromatography with ethyl acetate/hexane (2:98) afforded the product 1k in 67% yield. R f = 0.78 in 1:9 EtAc/Hexane FTIR (Neat): 3424, 2957, 2930, 2857, 1608, 1479, 1259, 967 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 5H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), 5.16 (m, 1H), 3.93 (s, 2H), 3.52 (s, 1H), 2.21 (s, 3H), 0.8 (s, 9H), 0.0 (s, 6H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 147.1, 146.9, 140.2, 139.8, 136.6, 136.5, 129.1, 128.6, 128.1, 127.2, 126.7, 122.5, 120.1, 116.3, 112.1, 48.8, 25.9, 21.1, 18.3, 4.2. HRMS: calcd. for C 28 H 35 NSi+H: ; found: Synthesis of 4-((4-Methylbenzyl)amino)-3-(1-enylvinyl)phenyl acetate (1n): Mixture of 4-((4-methylbenzyl)amino)-3-(1-phenylvinyl)phenol (300 mg, mmol, 1.0 equiv), acetic anhydride (0.1 ml, 1.04 mmol) and dimethylamino pyridine (catalytic amount) in pyridine (10 ml) was stirred at room temperature for 3 h. After completion of the reaction, pyridine was evaporated, dissolved with EtAc and washed with water. rganic layer was evaporated and the resultant crude was purified through column chromatography using ethyl acetate/hexane (2:98) to obtain title compound (258 mg, 76%). 36

37 R f = 0.66 in 1:9 EtAc/Hexane FTIR (Neat): 3425, 3059, 3028, 1758, 1607, 1509, 1367, 1213, 1188, 949 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 3H), (m, 2H), (m, 3H), 6.88 (d, 1H, J = 2.6 Hz), 6.69 (d, 1H, J = 8.7 Hz), 5.81 (d, 1H, J = 1.2 Hz), 5.41 (d, 1H, J = 1.1 Hz), 4.16 (s, 2H), 4.02 (s, 1H), 2.31 (s, 3H), 2.26 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 170.2, 146.4, 143.3, 141.6, 139.4, 136.7, 136.1, 129.2, 128.7, 128.3, 127.8, 127.1, 126.8, 123.4, 121.6, 116.9, 111.0, 48.1, 21,2, HRMS: calcd. for C 24 H 23 N 2 +H: ; found: Synthesis of 4-((4-methylbenzyl)amino)-3-(1-phenylvinyl)phenyl 4- methylbenzenesulfonate (1o): Mixture of 4-((4-methylbenzyl)amino)-3-(1-phenylvinyl)phenol (500 mg, mmol, 1 equiv), DMAP (catalytic amount) and Et 3 N (0.44 ml, mmol, 2 equiv) in dry CH 2 Cl 2 (10 ml) were stirred at room temperature for 5 min. Tosyl chloride (302 mg, mmol, 1 equiv) was added and continued stirring for 5 h. Next, the reaction mixture was diluted with 20 ml of DCM and washed with water followed by brine solution. rganic layer was dried over Na 2 S 4, evaporated and the crude was purified through column chromatography using ethyl acetate and hexane (3: 97) to obtain the title compound (565 mg, 76% yield). R f = 0.64 in 1:9 EtAc/Hexane 37

38 FTIR (Neat): 3426, 2928, 2875, 1601, 1510, 1370, 1191, 1166, 1092, 936 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 3H), (m, 4H), (m, 2H), 6.90 (dd, 1H, J = 2.8, 8.8 Hz), (m, 2H), 6.58 (d, 1H, J = 2.8 Hz), 6.46 (d, 1H, J = 8.8 Hz), 5.71 (d, 1H, J = 1.2 Hz), 5.2 (d, 1H, J = 1.2 Hz), 4.11(s, 2H), 3.98 (s, 1H), 2.40 (s, 3H), 2.30 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 146.0, 145.0, 144.2, 140.4, 139.0, 136.8, 135.7, 132.6, 129.6, 129.3, 128.8, 128.7, 128.4, 127.6, 127.0, 126.6, 124.3, 122.9, 117.1, 110.8, 47.9, 21.7, HRMS: calcd. for C 29 H 27 N 3 S+H: ; found: Synthesis of methyl 2-((4-methoxy-2-(1-phenylvinyl)phenyl)(4- methylbenzylamino)-2-phenylacetate (4b): In a oven-dried reaction tube, 1b (400 mg, 1.21 mmol, 1 equiv), Rh 2 (Ac) 4 (10.2 mg, 2 mol%) and CH 2 Cl 2 (8 ml) were added under argon atmosphere and kept at room temperature. Subsequently, Diazo ester 2b introduced slowly with syringe. After completion of the reaction, it was diluted with CH 2 Cl 2 and washed with brine solution. Evaporation of solvent followed by purification of the resultant crude through column chromatography using hexane/ethyl acetate with ratio (1:99), afforded coupled product 4b in 83% yield. R f = 0.64 in 1:9 EtAc/Hexane 38

39 FTIR (Neat): 3435, 2963, 2890, 1720, 1609, 1511, 1229, 1112, 908 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 6H), (m, 2H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), (m, 2H), 5.79 (d, 1H, J = 1.6 Hz), 5.49 (d, 1H, J = 1.6 Hz), 5.07 (d, 1H, J = 2.4 Hz), 4.40 (dd, 1H, J = 2.3, 14.6 Hz), 3.83 (s, 3H), 3.64 (dd, 1H, J = 2.3, 14.6 Hz), 3.55 (s, 3H), 2.31 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.0, 155.5, 150.1, 140.9, 140.3, 138.4(9), 138.4(8), 136.2, 133.6, 129.5, 129.0, 128.4, 128.3, 128.1, 128.0, 127.6, 127.1, 123.9, 118.0, 116.6, 112.6, 68.6, 55.3, 52.2, 51.5, HRMS: calcd. for C 32 H 31 N 3 +Na: ; found:

40 19. ptimization Table S1: Transition metal catalyzed carbenylative amination Entry Catalyst (mol%) Additives (1 equiv) Temp ( C) Yield of 3b Yield of 4a (%) a (%) a 1 Rh 2 (Ac) 4 (6) [Cp*RhCl 2 ] 2 (4) Cu(Ac) 2.H 2 (10) Cu(Ac) 2 (10) CuI(10) Pd(Ac) 2 (6) Pd(P 3 ) 2 Cl 2 (6) PdCl 2 (5) Pd(P 3 ) 2 Cl 2 (5) Pd(CH 3 CN) 2 Cl 2 (5) Pd(CN) 2 Cl 2 (5) [Ru(p-cymene)Cl 2 ] 2 (6) [Pd(Cinnamyl)Cl] 2 (3) [Pd(Cinnamyl)Cl] 2 (3) Cs 2 C [Pd(Cinnamyl)Cl] 2 (3) K 2 C [Pd(Cinnamyl)Cl] 2 (3) CuI [Pd(Cinnamyl)Cl)] 2 (3) Cu(Ac) 2.H [Pd(Cinnamyl)Cl)] 2 (3) CuCl [Pd(Cinnamyl)Cl)] 2 (3) CuBr [Pd(Cinnamyl)Cl)] 2 (3) Cu(Tf) [Pd(Cinnamyl)Cl)] 2 (3) AgF [Pd(Cinnamyl)Cl)] 2 (3) AgAc [Pd(Cinnamyl)Cl)] 2 (4)

41 23 [Pd(Cinnamyl)Cl)] 2 (6) [Pd(Cinnamyl)Cl)] 2 (6) [Pd(Cinnamyl)Cl)] 2 (6) [Pd(Cinnamyl)Cl)] 2 (6) b - 27 [Pd(Cinnamyl)Cl)] 2 (6) Reaction conditions: aniline 1b (1 equiv), diazo compound 2a (2 equiv), additive (1 equiv), temp, toluene, 8 h. a All are isolated Yields, b Xylene was used Table S2: Ligand screening Entry Ligand (10 mol%) Yield of 3b (%) a 28 P (2-Furyl) 3 P (o-tolyl) 3 P X-os S-os DPPE Ad 2 PBu (S)- Binap (R)- Binap 49 Reaction conditions: aniline 1b (1 equiv), diazo compound 2a (2 equiv), ligand (10 mol%), 100 C, toluene, 8 h. a All are isolated Yields. 41

42 20. Typical procedure for the synthesis of substituted indolines (3): Substituted 2-vinyl anilines 1 (0.15 mmol, 1 equiv), [Pd(cinnamyl)Cl] 2 ( mmol, 6 mol%) and toluene (1.5 ml) were added under argon atmosphere to an over dried 10 ml reaction tube equipped with stir bar. The reaction tube was sealed and kept at 120 C in pre-heated oil bath. Subsequently, the solution of diazo esters 2 (0.36 mmol, 2 equiv) in toluene (0.1 ml) was introduced slowly through syringe pump (addition rate = ml/min). After the addition of diazo ester, the reaction mixture was stirred for 8 h at same temperature. After the TLC analysis, it was cooled to room temperature and solvent was removed under reduced pressure. Purification of the resultant crude through column chromatography using hexane/ethyl acetate mixture as eluent afforded indoline derivatives 3 in high yield and purity. 21. Properties of isolated indolines (3): Indoline (3b): According to the general procedure the product was isolated in 84% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. 42

43 ysical State: semi solid Colour: light green R f = 0.60 in 1:9 EtAc/Hexane FTIR (Neat): 3054, 2995, 2947, 1729, 1599, 1492, 1442, 1264, 1211, 1039, 802 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 1H), (m, 5H), (m, 2H), (m, 1H), 6.60 (s, 1H), (m, 1H), (m, 2H), 3.76 (s, 3H), 3.73 (s, 3H), 2.41 (s, 3H), 2.01 (s, 3H). 13 C{ 1 H} NMR (400 MHz, CDCl 3, 24 C): δ 171.5, 153.4, 145.4, 142.1, 137.3, 136.8, 136.2, 135.9, 129.2, 129.0, 127.9, 127.4, 127.2, 126.9, 126.4, 126.1, 112.3, 111.1, 107.7, 88.3, 58.7, 55.8, 52.1, 51.7, 24.3, HRMS: calcd. for C 32 H 31 N 3 +H: ; found: Indoline (3f): According to the general procedure the product was isolated in 71% yield using mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: solid Colour: green Mp: 102 ºC R f = 0.67 in 1:9 EtAc/Hexane 43

44 FTIR (KBr): 3054, 2985, 1730, 1601, 1487, 1442, 1264, 896 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), 7.10 (td, 1H, J = 1.2, 7.6 Hz), (m, 1H), (m, 8H), 6.77 (td, 1H, J = 0.9, 7.3 Hz), 6.35 (d, 1H, J = 7.6 Hz), 4.37 (s, 2H), 3.72 (s, 3H), 2.38 (s, 3H), 1.97 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.5, 151.2, 142.0, 136.9, 136.1, 136.0, 135.6, 129.2, 128.1, 127.9, 127.5, 127.3, 126.9, 126.4, 126.2, 123.9, 118.7, 107.4, 88.2, 59.1, 52.1, 51.8, 25.1, HRMS: calcd. for C 31 H 29 N 2 +H: ; found: Indoline (3g): According to the general procedure the product was isolated in 73% yield using mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: solid Colour: light yellow Mp: 110 ºC R f = 0.66 in 1:9 EtAc/Hexane FTIR (KBr): 3054, 3022, 2948, 1729, 1611, 1498, 1345, 1264, 1009 cm 1. 44

45 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 9H), 6.79 (s, 1H), 6.31 (d, 1H, J = 7.8 Hz), 4.40 (s, 2H), 3.77 ( s, 3H), 2.43 ( s, 3H), 2.30 (s, 3H), 2.03 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 149.0, 142.2, 136.9, 136.3, 135.9, 129.2, 128.3, 128.3, 128.0, 127.9, 127.5, 127.2, 126.9, 126.4, 126.1, 124.7, 107.3, 88.3, 58.9, 52.1, 51.72, 24.87, 21.2, HRMS: calcd. for C 32 H 31 N 2 +H: ; found: Indoline (3h): According to the general procedure the product was isolated in 76% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: crystalline solid Colour: colourless Mp: 105 ºC R f = 0.66 in 1:9 EtAc/Hexane FTIR (KBr): 3055, 2958, 2866, 1729, 1611, 1492, 1442, 1348, 1265, 1009 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 1H), (m, 9H), 6.27 (d, 1H, J = 8.2 Hz), 4.34 (m, 2H), 3.73 (s, 3H), 2.39 (s, 3H), 1.98 (s, 3H), 1.26 (s, 9H). 45

46 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 148.9, 142.3, 141.7, 137.1, 136.5, 136.9, 135.2, 129.3, 129.2, 128.0, 127.5, 127.2, 126.9, 126.5, 126.1, 124.3, 121.3, 109.5, 88.4, 59.3, 52.3, 51.6, 34.3, 31.8, 25.2, HRMS: calcd. for C 35 H 37 N 2 +H: ; found: Indoline (3i): According to the general procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: semi solid Colour: colourless R f = 0.67 in 1:9 EtAc/Hexane FTIR (neat): 3040, 2949, 2354, 1729, 1605, 1485, 1446, 1342, 1250, 1114, 1009, 897, 810 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 5H), (m, 6H), (m, 8H), 6.39 (d, 1H, J = 8.1 Hz), 4.39 (s, 2H), 3.73 (s, 3H), 2.37 (s, 3H), 1.99 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.4, 150.8, 141.7, 141.4, 136.8, 136.2, 136.1, 136.0, 131.8, 129.2, 128.6, 127.9, 127.6, 127.4, 127.0(9), 127.0(2), 126.4(7), 126.4(3), 126.3, 126.1, 122.9, 107.5, 88.4, 59.4, 52.2, 51.8, 25.4, HRMS: calcd. for C 37 H 33 N 2 +Na: ; found:

47 Indoline (3j): According to the general procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: solid Colour: light yellow Mp: 134 ºC R f = 0.59 in 1:9 EtAc/Hexane FTIR (KBr): 3055, 2859, 1727, 1599, 1492, 1375, 1265, 1079, 896 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 7H), (m, 4H), (m, 1H), (m, 5H), (m, 2H), (m, 1H), 6.64 (m, 1H), 6.24 (d, 1H, J = 8.4 Hz), 4.93 (m, 2H), 4.29 (m, 2H), 3.73 (s, 3H), 2.38 (s, 3H), 1.97 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 152.7, 145.7, 142.0, 137.6, 137.3, 136.8, 136.2, 136.0, 129.2, 129.1, 128.5, 128.0, 127.8, 127.7, 127.4, 127.3, 126.9, 126.4, 126.2, 113.7, 112.3, 107.7, 88.4, 71.0, 58.8, 52.2, 51.7, 24.4, HRMS: calcd. for C 38 H 35 N 3 +H: ; found:

48 Indoline (3k): According to the general procedure the product was isolated in 68 % yield using the mixture of ethyl acetate/hexanes (8:92) as an eluent for column chromatography. ysical State: gummy liquid Colour: colourless R f = 0.61 in 1:9 EtAc/Hexane FTIR (Neat): 3055, 2955, 2857, 1729, 1598, 1488, 1264, 951 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 3H), (m, 6H), (m, 8H), 6.51 (dd, 1H, J = 2.4, 8.3 Hz), 6.39 (d, 1H, J = 2.3 Hz), 6.11 (d, 1H, J = 8.3 Hz), 4.21 (m, 2H), 3.64 (s, 3H), 2.31 (s, 3H), 1.89 (s, 3H), 0.89 (s, 9H), 0.07 (s, 6H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 148.5, 145.8, 142.1, 136.9, 136.9, 136.3, 135.9, 129.2, 129.1, 128.0, 127.4, 127.2, 126.8, 126.4, 126.1, 118.7, 116.4, 107.7, 88.3, 58.7, 52.2, 51.5, 25.8, 24.5, 21.2, 18.2, 4.3. HRMS: calcd. for C 37 H 43 N 3 Si+H: ; found:

49 Indoline (3l): According to the general procedure the product was isolated in 51% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. ysical State: gummy liquid Colour: dark green R f = 0.55 in 1:9 EtAc/Hexane FTIR (Neat): 3054, 2927, 1730, 1610, 1476, 1263, 1038, 939 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 1H), (m, 5H), (m, 2H), 6.42 (s, 1H), 5.96 (s, 1H), 5.85 and 5.82 (AB q, 2H, J = 1.4 Hz), 4.26 (m, 2H), 3.73 (s, 3H), 2.36 (s, 3H), 1.91 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 147.2, 146.4, 142.2, 140.2, 136.7, 136.1, 136.0, 129.3, 129.1, 128.0, 127.5, 127.3, 127.2, 126.9, 126.4, 126.2, 105.4, 100.8, 91.7, 88.6, 58.5, 52.3, 51.8, 24.6, HRMS: calcd. for C 32 H 29 N 4 +H: ; found:

50 Indoline (3m): According to the general procedure the product was isolated in 69% yield using mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 119 ºC R f = 0.59 in 1:9 EtAc/Hexane FTIR (KBr): 3058, 3030, 2927, 1731, 1602, 1489, 1442, 1252, 1157, 1011 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 1H), (m, 5H), (m, 2H), (m, 1H), 6.63 (dd, 1H, J = 2.5, 8.3 Hz), (m, 1H), (m, 2H), 3.72 (s, 3H), 2.37 (s, 3H), 1.95 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.4, 158.4, 156.0, 147.4, 141.6, (d, J = 7.3 Hz), 136.5, 136.2, 135.8, 129.3, 128.9, 127.9, 127.6, 127.4, 127.0, 126.4, (d, J = 22.8 Hz), (d, J = 24.5 Hz), (d, J = 7.8 Hz), 88.6, 58.7, 52.2, 51.8, 24.4, HRMS:calcd. for C 31 H 28 N 2 F+H: ; found:

51 Indoline (3n): According to the general procedure the product was isolated in 69% yield using mixture of ethyl acetate/hexanes (5:95) as an eluent for column chromatography. ysical State: Gummy liquid Colour: light green R f = 0.57 in 1:9 EtAc/Hexane FTIR (Neat): 3055, 2969, 1732, 1604, 1492, 1370, 1264, 1151, 1010 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.30 (d, 2H, J = 7.9 Hz), (m, 5H), (m, 1H), (m, 6H), 6.80 (dd, 1H, J = 2.3, 8.4 Hz), 6.62 (d, 1H, J = 2.3 Hz), 6.27 (d, 1H, J = 8.4 Hz), 4.35 and 4.30 (AB q, 2H, J = 17.1 Hz), 3.72 (s, 3H), 2.37 (s, 3H), 2.20 (s, 3H), 1.95 (s, 3H) 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.3, 170.1, 148.8, 143.4, 141.3, 138.9, 136.6, 129.8, 129.1, 128.6, 128.5, 128.2, 127.9, 127.6, 127.0, 126.5, 126.4, 120.7, 117.8, 107.1, 88.5, 59.0, 52.9, 52.5, 51.9, 25.2, HRMS:calcd. for C 33 H 31 N 4 +Na: ; found:

52 Indoline (3o): According to the general procedure the product was isolated in 80% yield using mixture of ethyl acetate/hexanes (3:97) as an eluentfor column chromatography. ysical State: semi solid Colour: green R f = 0.48 in 1:9 EtAc/Hexane FTIR (Neat): 2944, 2887, 1732, 1601, 1486, 1443, 1371, 1181, 1092, 929 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 4H), (m, 3H), (m, 5H), 6.89 (dd, 1H, J = 2.4, 8.5 Hz), (m, 2H), 6.27 (d, 1H, J = 2.3 Hz), 6.20 (d, 1H, J = 8.5 Hz), 4.33 and 4.29 (AB q, 2H, J = 17.1 Hz), 3.72 (s, 3H), 2.38 (s, 3H), 2.36 (s, 3H), 1.81 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.0, 150.0, 144.9, 142.2, 141.0, 136.6, 136.2, 135.4, 132.4, 129.5, 129.3, 128.8, 128.7, 127.7, 127.5, 127.5, 126.9, 126.4, 126.3, 122.3, 118.4, 107.3, 88.4, 58.7, 52.1, 51.8, 24.8, 21.7, HRMS: calcd. for C 38 H 35 N 5 S+H: ; found:

53 Indoline (3p): According to the general procedure the product was isolated in 80% yield using mixture of ethyl acetate/hexanes (8:92) as an eluent for column chromatography. ysical State: semi solid Colour: dark red R f = 0.55 in 1:9 EtAc/Hexane FTIR (Neat): 3070, 2910, 1847, 1737, 1722, 1604, 1445, 1370, 1256, 1138, 1092, 924 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.87 (dd, 1H, J = 1.7, 8.3 Hz), 7.56 (d, 1H, J = 1.6 Hz), (m, 10H), (m, 10H), 6.32 (d, 1H, J = 8.3 Hz), 4.47 and 4.42 (AB q, 2H, J = 16.9 Hz), (m, 2H), 3.69 (s, 3H), 3.54 (s, 3H), 1.29 (t, 3H, J = 7.1 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 170.9, 168.5, 166.9, 155.1, 141.0, 138.2, 137.6, 136.1, 135.4, 131.6, 129.1, 128.9, 128.6, 128.0, 127.7, 127.6, 127.1, 126.8, 126.5, 126.4, 125.8, 121.0, 106.5, 88.6, 60.4, 59.0, 52.3, 52.2, 52.0, 25.7, HRMS: calcd. for C 33 H 31 N 4 +Na: ; found:

54 Indoline (3q): According to the general procedure the product was isolated in 77% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 101 ºC R f = 0.69 in 1:9 EtAc/Hexane FTIR (KBr): 3051, 2924, 2859, 1731, 1591, 1487, 1350, 1258, 1124 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 3H), (m, 5H), (m, 6H), 6.41 (s, 1H), 6.11 (s, 1H), (m, 2H), 3.72 (s, 3H), 2.40 (s, 3H), 2.27 (s, 3H), 2.02 (s, 3H), 1.78 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.4, 151.7, 141.3, 137.9, 137.4, 136.5, 135.6, 133.7, 129.5, 129.0, 128.6, 128.2, 127.5, 127.2, 126.7, 126.4, 125.9, 122.4, 105.7, 88.1, 59.1, 52.4, 51.6, 23.4, 21.7, 21.2, HRMS: calcd. for C 33 H 33 N 2 +H: ; found:

55 Indoline (3r): According to the general procedure the product was isolated in 52% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: liquid Colour: colourless R f = 0.72 in 1:9 EtAc/Hexane FTIR (Neat): 3384, 3029, 2931, 2854, 2805, 1953, 1882, 1817, 1731, 1602, 1496, 1446, 1380, 1348, 1243, 1104, 1023, 959, 806 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), 7.21 (dd, 1H, J = 1.7, 8.2 Hz), (m, 3H), (m, 3H), (m, 3H), (m, 6H), (m, 1H), 6.31 (d, 1H, J = 8.2 Hz) 4.37 (s, 2H), 3.72 (s, 3H), 2.36 (s, 3H), 1.98 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.3, 151.2, 141.7, 138.1, 136.6, 136.3, 136.1, 135.8, 129.3, 129.1, 128.6, 128.5, 127.9, 127.6, 127.5, 127.0, 126.8, 126.4, (2), 126.1, 124.7, 121.8, 107.4, 88.4, 59.1, 52.0, 51.9, 25.4, HRMS: calcd. for C 39 H 35 N 2 +H: ; found:

56 Indoline (3u): According to the general procedure the product was isolated in 69% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: liquid Colour: colourless R f = 0.60 in 1:9 EtAc/Hexane FTIR (Neat): 3051, 2948, 2849, 1730, 1602, 1498, 1440, 1227, 1164, 1034 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), 7.34 (t, 2H, J = 7.4 Hz), (m, 1H), 7.14 (d, 2H, J = 7.8 Hz), (m, 1H), (m, 5H), (m, 2H), 6.61 (dd, 1H, J = 2.0, 8.4 Hz), 6.53 (m, 1H), 6.19 (d, 1H, J = 8.4 Hz), 4.30 (m, 2H), 3.68 (s, 3H), 3.67 (s, 3H), 1.94 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 153.5, 145.3, 142.0, 139.4, 137.2, 136.8, 129.1, 128.5, 128.0, 127.5, 127.3, 126.9, 126.5(8), 125.5(5), 126.2, 112.4, 111.2, 107.6, 88.3, 58.9, 55.9, 52.4, 51.7, 24.5 HRMS: calcd. for C 31 H 29 N 3 +H: ; found:

57 Indoline (3v): According to the general procedure the product was isolated in 77% yield using the mixture of ethyl acetate/hexanes (4:96) as an eluent for column chromatography. ysical State: gummy liquid Colour: light green R f = 0.56 in 1:9 EtAc/Hexane FTIR (Neat): 3055, 2989, 1728, 1605, 1493, 1265, 1168, 1137, 898 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.35 (d, 2H, J = 8.6 Hz), 7.15 (d, 2H, J = 7.6 Hz), (m, 10H), 6.63 (dd, 1H, J = 2.5, 8.4 Hz), 6.54 (d, 1H, J = 2.5 Hz), 6.21 (d, 1H, J = 8.4 Hz), 4.24 (m, 2H), 3.83 (s, 3H), 3.72 (s, 3H), 3.69 (s, 3H), 1.95 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 158.3, 153.5, 145.4, 142.1, 137.3, 136.8, 131.3, 129.1, 128.0, 127.5, 127.4, 127.3, 126.9, 126.2, 114.0, 112.4, 111.2, 107.7, 88.3, 58.8, 55.9, 55.3, 51.8, 51.7, HRMS: calcd. for C 32 H 31 N 4 +H: ; found:

58 Indoline (3x): According to the general procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. ysical State: liquid Colour: light orange R f = 0.53 in 1:9 EtAc/Hexane FTIR (Neat): 3056, 2926, 2855, 1730, 1599, 1493, 1267, 1042 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.30 (m, 1H), (m, 2H), (m, 1H), (m, 5H), (m, 3H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), 3.63 (s, 3H), 3.62 (s, 3H), 1.82 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 153.7, 153.0, 145.4, 142.5, 141.4, 137.2, 136.4, 128.8, 128.1, 127.4, 127.3, 126.9, 126.1, 112.5, 111.0, 110.5, 107.5, 106.8, 88.1, 58.3, 55.9, 51.8, 46.3, HRMS: calcd. for C 29 H 27 N 4 +H: ; found:

59 Indoline (3z): According to the general procedure the product was isolated in 56% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: liquid Colour: yellow R f = 0.61 in 1:9 EtAc/Hexane FTIR (Neat): 2980, 2939, 1725, 1595, 1489, 1375, 1276, 1035 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 1H), (m, 4H), (m, 3H), (m, 2H), (m, 3H), 3.65 (s, 3H), 3.61 (s, 3H), (m, 1H), 1.79 (s, 3H), 1.29 (d, 3H, J = 6.9 Hz), 1.10 (d, 3H, J = 6.6 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.1, 152.8, 144.3, 142.9, 138.6, 137.5, 128.4, 128.2, 126.9, 125.7, 111.7, 111.1, 108.2, 87.1, 57.3, 55.9, 51.5, 47.1, 22.3, 21.4, HRMS: calcd. for C 27 H 30 N 3 +H: ; found: Indoline (3aa): 59

60 According to the general procedure the product was isolated in 73% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: semi solid Colour: colourless R f = 0.59 in 1:9 EtAc/Hexane FTIR (Neat): 3055, 2953, 2874, 1725, 1596, 1485, 1265, 1035, 899 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 1H), (m, 4H), (m, 3H), (m, 1H), (m, 4H), 3.65 (s, 3H), 3.59 (s, 3H), (m, 1H), (m, 2H), 1.80 (s, 3H), (m, 3H), (m, 1H), (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.3, 152.9, 144.5, 142.5, 138.9, 137.3, 128.4, 126.9, 126.9, 125.6, 111.6, 111.1, 107.9, 87.4, 57.7, 57.0, 55.9, 51.7, 29.0, 25.8, 24.6, 23.2, HRMS: calcd. for C 29 H 32 N 3 +H: ; found: Indoline (3ab): According to the general procedure the product was isolated in 71% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: semi solid Colour: colourless R f = 0.60 in 1:9 EtAc/Hexane 60

61 FTIR (Neat): 3054, 2987, 2935, 1724, 1489, 1206, 1037, 895 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 3H), (m, 5H), (m, 2H), (m, 3H), 3.74 (s, 3H), 3.71 (s, 3H), (m, 1H), (m, 2H), 1.88 (s, 3H), (m, 6H), (m, 2H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.5, 152.6, 144.2, 143.7, 138.4, 137.8, 128.4, 128.1, 126.9, 126.8, 125.6, 111.7, 110.9, 108.4, 86.8, 57.3, 56.6, 55.9, 51.4, 31.1, 27.1, 26.7, 26.1, HRMS: calcd. for C 30 H 33 N 3 +H: ; found: Indoline (3ac): According to the general procedure the product was isolated in 41% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: gummy liquid Colour: light yellow R f = 0.60 in 1:9 EtAc/Hexane FTIR (Neat): 3055, 2932, 1724, 1596, 1487, 1264, 1036, 896 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 1H), (m, 4H), (m, 3H), 6.70 (dd, 1H, J = 2.6, 8.4 Hz), 6.62 (d, 1H, J = 8.4 Hz), 6.56 (d, 1H, J = 2.5 Hz), (m, 61

62 2H), 3.74 (s, 3H), 3.66 (s, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 1.91 (s, 3H), (m, 2H), (m, 7H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.2, 152.8, 144.6, 138.9, 137.4, 128.8, 128.3, 128.1, 126.9, 126.9, 125.6, 111.6, 110.8, 108.4, 87.3, 56.9, 55.9, 51.4, 33.3, 28.6, 27.7, 27.3, 26.9, HRMS: calcd. for C 31 H 35 N 3 +H: ; found: Indoline (3af): According to the general procedure the product was isolated in 80% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 101 ºC R f = 0.59 in 1:9 EtAc/Hexane FTIR (KBr): 3055, 2924, 2859, 1727, 1601, 1513, 1493, 1348, 1266, 1041 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.29 (d, 2H, J = 8.0 Hz), 7.15 (d, 2H, J = 7.9 Hz), (m, 5H), (m, 2H), 6.76 (d, 2H, J = 8.0 Hz), 6.61 (dd, 1H, J = 2.6, 8.4 Hz), 6.52 (d, 62

63 1H, J = 2.5 Hz), 6.19 (d, 1H, J = 8.4 Hz), 4.25 (s, 2H), 3.69 (s, 3H), 3.68 (s, 3H), 2.35 (s, 3H), 2.16 (s, 3H), 1.93 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.7, 153.4, 145.5, 142.2, 137.4, 137.0, 136.4, 136.0, 133.8, 129.2(7), 129.2(3), 128.2, 127.9, 126.9, 126.5, 126.2, 112.4, 111.2, 107.6, 88.3, 58.8, 56.0, 52.2, 51.6, 24.4, 21.2, HRMS: calcd. for C 33 H 33 N 3 +H: ; found: Indoline (3ag): According to the general procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: semi solid Colour: white R f = 0.59 in 1:9 EtAc/Hexane FTIR (Neat): 2950, 2883, 1719, 1601, 1508, 1463, 1314, 1115, 1031 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 2H), (m, 5H), (m, 2H), 6.64 (dd, 1H, J = 2.6, 8.4 Hz), 6.59 (d, 1H, J = 2.5 Hz). 63

64 6.22 (d, 1H, J = 8.4 Hz), 4.33 & 4.28 (AB q, 2H, J = 16.7 Hz), 3.72 (s, 3H), 3.71 (s, 3H), 2.39 (s, 3H), 1.96 (s, 3H), 1.22 (s, 9H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 153.4, 149.1, 145.4, 138.9, 137.3, 137.0, 136.3, 135.9, 129.2, 128.5, 128.0, 127.3, 127.1, 126.4, 123.7, 112.3, 111.2, 107.6, 88.4, 58.7, 55.9, 52.1, 51.6, 34.2, 31.3, 24.1, HRMS: calcd. for C 36 H 39 N 3 +H: ; found: Indoline (3ah): According to the general procedure the product was isolated in 86% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: liquid Colour: black R f = 0.59 in 1:9 EtAc/Hexane FTIR (Neat): 3047, 2926, 2843, 1730, 1600, 1496, 1232, 1164, 1041 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.32 (d, 2H, J = 7.8 Hz), (m, 4H), (m, 1H), (m, 3H), (m, 2H), (m, 3H), 6.54 (d, 1H, J = 2.2 Hz), 6.25 (d, 1H, J = 8.4 Hz), 4.30 (s, 3H), 3.73 (s, 3H), 3.72 (s, 3H), 2.39 (s, 3H), 1.96 (s, 3H). 64

65 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.5, (d, J = Hz), 153.5, 145.3, (d, J = 3.2 Hz), 137.0, 136.7, (d, J = 13.8 Hz), (d, J = 7.9 Hz), 129.2, 127.9, 127.6, 127.5, 126.4, 113.7, 113.5, 112.4, 111.1, 107.8, 88.2, 58.3, 55.9, 52.1, 51.7, 24.5, HRMS: calcd. for C 32 H 30 N 3 F+Na: ; found: Indoline (3ai): According to the general procedure the product was isolated in 75% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: Liqiud Colour: Colourless R f = 0.69 in 1:9 EtAc/Hexane FTIR (Neat): 3069, 2933, 2888, 2376, 1958, 1884, 1731, 1604, 1483, 1353, 1062, 900 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), 7.39 (m, 2H), (m, 3H), (m, 5H), 6.96 (d, 1H, J = 5.0 Hz), 6.76 (td, 1H, J = 0.4, 7.4 Hz), (m, 1H), (m, 1H), 6.29 (d, 1H, J = 7.8 Hz), 4.36 and 4.31 (AB q, 2H, J = 17.1 Hz), 3.71 (s, 3H), 1.97 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.2, 150.7, 147.5, 139.0, 136.6, 135.4, 132.0, 128.6, 128.5, 127.7, 127.6, 127.0, 126.6, 126.5, 125.6, 124.7, 123.8, 118.8, 107.7, 88.1, 57.1, 52.4, 51.8, HRMS: calcd. for C 28 H 25 N 2 S+H: ; found:

66 Indoline (3aj): According to the general procedure the product was isolated in 75% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: Liqiud Colour: Colorless R f = 0.59 in 1:9 EtAc/Hexane FTIR (Neat): 3018, 2929, 2661, 2366, 1994, 1729, 1602, 1482, 1224, 1031, 1031 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), 7.20 (s, 1H), 7.18 (s, 1H), (m, 5 H), (m, 2H), (m, 1H), 5.24 (t, 1H, J = 3.5 Hz), 4.13 (s, 2H), 3.63 (s, 3H), 3.57 (s, 3H), 2.28 (s, 3H), (m, 3H), 1.54 (s, 3H), (m, 1H), (m, 2H), (m, 1H), (m, 1H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.9, 153.3, 146.0, 138.8, 137.4, 137.3, 136.0, 129.3, 128.9, 127.3, 127.0, 126.6, 126.5, 111.4, 111.0, 107.9, 88.0, 59.6, 55.6, 52.9, 51.6, 26.2, 25.8, 23.2, 22.8, 21.8, HRMS: calcd. for C 32 H 35 N 3 +Na: ; found:

67 Indoline (3ak): According to the general procedure the product was isolated in 56% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: Liqiud Colour: Colourless R f = 0.71 in 1:9 EtAc/Hexane FTIR (KBr): 3054, 2941, 2867, 2629, 1954, 1805, 1732, 1599, 1476, 1212, 1013 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), 6.74 (td, 1H, J = 0.9, 7.4 Hz), 6.16 (d, 1H, J = 7.6 Hz), 4.20 and 4.14 (AB q, 2H, J = 16.8 Hz), 3.65 (s, 3H), 1.48 (s, 3H), (m, 1H), (m, 2H), (m, 3H), 0.67 (t, 3H, J = 7.1 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.1, 150.9, 138.9, 136.5, 128.6, 128.3, 127.8, 127.7, 127.4, 126.6, 122.4, 118.4, 108.3, 88.3, 52.5, 52.4, 51.6, 38.3, 26.3, 23.4, 21.8, HRMS: calcd. for C 28 H 31 N 2 +Na: ; found:

68 Indoline (3al): According to the general procedure the product was isolated in 58% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: Liqiud Colour: Colourless R f = 0.70 in 1:9 EtAc/Hexane FTIR (Neat): 3037, 2943, 2878, 2640, 2150, 1730, 1599, 1471, 1347, 1216, 1013, 895 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), 7.36 (t, 2H, J = 7.3 Hz), (m, 4H), (m, 2H), 6.74 (t, 1H, J = 7.3 Hz), 6.15 (d, 1H, J = 7.7 Hz), 4.20 and 4.14 (AB q, 2H, J = 16.8 Hz), 3.65 (s, 3H), 1.47 (s, 3H), (m, 1H), (m, 6H), (m, 3H), 0.77 (t, 3H, J = 7.2 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.1, 150.9, 138.9, 136.5, 128.6, 128.3, 127.8, 127.7, 127.4, 126.6, 122.4, 118.4, 108.3, 88.3, 52.6, 52.4, 51.6, 38.7, 31.8, 30.0, 24.1, 22.6, 21.9, HRMS: calcd. for C 30 H 35 N 2 +Na: ; found:

69 Indoline (3am): According to the general procedure the product was isolated in 47% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: gummy liqiud Colour: Colourless R f = 0.71 in 1:9 EtAc/Hexane FTIR (Neat): 3037, 2947, 2865, 1733, 1600, 1478, 1351, 1256, 1014, 739 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), 6.73 (t, 1H, J = 7.3 Hz), 6.15 (d, 1H, J = 7.7 Hz), 4.20, 4.15 (AB q, 2H, J = 16.6 Hz), 3.64 (s, 3H), 1.47 (s, 3H), (m, 1H), (m, 2H), (m, 2H), (m, 6H) 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.0, 150.9, 138.9, 136.5, 128.7, 128.6, 128.3, 127.8(3), 127.8(0), 127.4, 126.6, 125.4, 122.3, 118.4, 108.2, 88.2, 52.5, 52.4, 51.6, 36.6, 32.9, 28.6, 22.6, 22.3, HRMS: calcd. for C 29 H 33 N 2 +H: ; found:

70 Indoline (3an): According to the general procedure the product was isolated in 91% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: gummy liquid Colour: white R f = 0.69 in 1:9 EtAc/Hexane FTIR (Neat): 3059, 3028, 2969, 2872, 1731, 1603, 1487, 1352, 1262, 1093 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.39 (d, 2H, J = 7.1 Hz), (m, 4H), (m, 4H), (m, 2H), (m, 1H), 6.08 (d, 1H, J = 7.6 Hz), 4.21 and 3.91 (AB q, 2H, J = 16.4 Hz), 3.70 (s, 3H), 1.43 (s, 3H), 1.07 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.9, 150.2, 139.2, 137.6, 137.1, 128.5, 128.1, 127.9, 127.7, 127.5, 126.7, 126.6, 121.0, 118.7, 107.6, 87.0, 52.1, 51.6, 49.6, 27.2, HRMS: calcd. for C 25 H 25 N 2 +H: ; found: Indoline (3ao): 70

71 According to the general procedure the product was isolated in 61% yield using the mixture of ethyl acetate/hexanes (1:99) as an eluent for column chromatography. ysical State: semi solid Colour: white R f = 0.70 in 1:9 EtAc/Hexane FTIR (Neat): 3061, 2949, 2881, 2624, 2525, 2358, 2118, 1923, 1737, 1602, 1478, 1146 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 5H), (m, 1H), 7.04 (d, 1H, J = 7.1 Hz), 6.93 (t, 1H, J = 7.5 Hz), 6.71 (t, 1H, J = 7.3 Hz), 6.08 (d, 1H, J = 7.8 Hz), 4.39, 3.90 (AB q, 2H, J = 16.2 Hz), 3.85 (q, 1H, J = 7.0 Hz), 3.74 (s, 3H), 1.42 (d, 3H, J = 7.0 Hz). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 172.0, 150.0, 140.1, 138.9, 132.8, (8), (6), 128.1, 127.9, 127.0, 126.9, 126.7, 122.1, 118.5, 108.1, 83.6, 51.7, 50.9, 48.6, HRMS: calcd. for C 24 H 24 N 2 +H: ; found: Indoline (3aq): According to the general procedure the product was isolated in 71% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: solid Colour: colourless Mp: 128 ºC 71

72 R f = 0.71 in 1:9 EtAc/Hexane FTIR (KBr): 2924, 2853, 1730, 1601, 1485, 1353, 1254, 1120, 1042 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.42 (d, 2H, J = 7.4 Hz), (m, 2H), (m, 4H), 7.13 (m, 1H), 6.99 (td, 1H, J = 1.2, 7.6 Hz), 6.94 (m, 1H), 6.73 (m, 1H), 6.13 (d, 1H, J = 7.7 Hz), 5.73 (ddt, 1H, J = 6.4, 10.2, 17.2 Hz), 4.94 (m, 2H), 4.28 and 3.73 (AB q, 2H, J = 16.2 Hz), 3.81 (s, 3H), (m, 3H), (m, 1H), (m, 1H), 1.23 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.8, 151.2, 139.8, 139.0, 137.4, 134.1, 128.4, 128.3, 128.1, 127.4, 126.8, 126.5, 123.0, 118.0, 114.4, 107.1, 87.7, 53.0, 52.9, 51.7, 38.9, 29.2, HRMS: calcd. for C 28 H 29 N 2 +H: ; found: Indoline (3at): According to the general procedure the product was isolated in 83% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: gummy liquid Colour: light green R f = 0.60 in 1:9 EtAc/Hexane FTIR (Neat): 3057, 2922, 2851, 1729, 1599, 1493, 1264, 1041 cm 1. 72

73 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 4H), (m, 1H), (m, 7H), 6.61 (dd, 1H, J = 2.2, 8.4 Hz), 6.52 (d, 1H, J = 2.2 Hz), 6.20 (d, 1H, J = 8.4 Hz), 4.29 (s, 2H), (m, 2H), 3.67 (s, 3H), 2.34 (s, 3H), 1.95 (s, 3H), 1.07 (t, 3H, J = 7.1 Hz). 13 C{ 1 H} NMR (400 MHz, CDCl 3, 24 C): δ 170.9, 153.4, 145.6, 142.0, 137.2, 137.0, 136.4, 135.9, 129.2, 129.1, 128.0, 127.4, 127.2, 126.9, 126.4, 126.2, 112.4, 111.3, 107.4, 88.1, 61.0, 59.0, 55.9, 52.2, 24.6, 21.2, HRMS: calcd. for C 33 H 33 N 3 +H: ; found: Indoline (3ax): According to the general procedure the product was isolated in 72% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 103 ºC R f = 0.59 in 1:9 EtAc/Hexane FTIR (KBr): 3056, 2929, 2833, 1728, 1600, 1494, 1376, 1267, 1156, 1038, 899 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 5H), (m, 2H), (m, 2H), 6.63 (dd, 1H, J = 2.5, 8.4 Hz), 6.55 (d, 1H, J = 2.5 Hz), 73

74 6.22 (d, 1H, J = 8.4 Hz), 4.28 (m, 2H), 3.72 (s, 3H), 3.70 (s, 3H), 2.38 (s, 3H), 2.18 (s, 3H), 1.96 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.7, 153.4, 145.5, 142.1, 137.3, 136.9, 136.4, 135.9, 133.7, 129.2, 129.1, 128.1, 127.9, 126.8, 126.4, 126.1, 112.3, 111.2, 107.6, 88.3, 58.7, 55.9, 52.1, 51.6, 24.4, 21.2, HRMS: calcd. for C 33 H 33 N 3 +H: ; found: Indoline (3ay): According to the general procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 146 ºC R f = 0.39 in 1:9 EtAc/Hexane FTIR (KBr): 3023, 2956, 2860, 1731, 1660, 1493, 1358, 1261, 1164, 1034 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.30 (d, 2H, J = 6.5 Hz), 7.16 (d, 2H, J = 6.8 Hz), 7.05 (d, 2H, J = 6.8 Hz), (m, 5H), (m, 2H), (m, 1H), (m, 1H), 5.85 (d, 1H, J = 1.3 Hz), 5.81 (d, 1H, J = 1.2 Hz), 4.30 (s, 2H), 3.71 (s, 3H), 2.36 (s, 3H), 1.88 (s, 3H), 1.17 (s, 9H) 74

75 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.7, 150.4, 147.2, 146.5, 142.3, 140.1, 136.1, 136.1(1), 133.6, 129.3, 129.1, 127.6, 127.2, 126.7, 126.4, 126.1, 124.4, 105.4, 100.8, 91.5, 88.6, 58.6, 52.2, 51.7, 34.3, 31.3, 24.4, HRMS: calcd. for C 36 H 37 N 4 +H: ; found: Indoline (3az): According to the general procedure the product was isolated in 69% yield using the mixture of ethyl acetate/hexanes (8:92) as an eluent for column chromatography. ysical State: gummy liquid Colour: colorless R f = 0.41 in 1:9 EtAc/Hexane FTIR (Neat): 2995, 2912, 2883, 1727, 1594, 1413, 1267, 1066, 877 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.30 (d, 2H, J = 7.9 Hz), (m, 3H), (m, 4H), 6.94 (dd, 1H, J = 0.8, 7.2 Hz), (m, 2H), 6.80 (td, 1H, J = 0.5, 7.3 Hz), 6.63 (d, 1H, J = 8.6 Hz), 6.54 (s, 1H), 6.42 (d, 1H, J = 7.7 Hz), 4.44 and 4.33 (AB q, 2H, J = 16.9 Hz), 3.78 (s, 3H), 3.71 (s, 3H), 3.19 (s, 3H), 2.37 (s, 3H), 1.96 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.9, 151.4, 148.1, 147.8, 142.5, 136.2, 135.9, 135.4, 129.1, 129.0, 128.8, 128.1, 126.9, 126.3, 126.2, 123.7, 120.5, 118.8, 112.1, 110.0, 107.3, 88.1, 58.7, 55.7, 55.7(5), 55.1, 51.7, 24.0,

76 HRMS: calcd. for C 33 H 33 N 4 +Na: ; found: Indoline (3ba): According to the general procedure the product was isolated in 70% yield using the mixture of ethyl acetate/hexanes (4:96) as an eluent for column chromatography. ysical State: gummy liquid Colour: colorless R f = 0.50 in 1:9 EtAc/Hexane FTIR (Neat): 2924, 2849, 1730, 1597, 1494, 1248, 1119, 1035cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 4H), (m, 3H), (m, 2H), (m, 2H), (m, 3H), (m, 2H), 6.52 (dd, 1H, J = 2.5, 8.4 Hz), (m, 2H), 6.44 (d, 1H, J = 2.5 Hz), 6.10 (d, 1H, J = 8.4 Hz), 4.84 (s, 2H), 4.17 (s, 2H), 3.61 (s, 3H), 3.60 (s, 3H), 2.27 (s, 3H), 1.83 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.8, 157.9, 153.4, 145.4, 142.2, 137.2, 137.1, 136.3, 136.0, 129.2, 129.1, 128.6, 127.9, 127.4, 126.9, 126.4, 126.2, 115.2, 113.8, 112.4, 111.2, 107.6, 88.08, 69.8, 58.8, 55.9, 52.0, 51.7, 24.3, 21.2 HRMS: calcd. for C 39 H 37 N 4 +Na: ; found:

77 Indoline (3bb): According to the general procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (5:95) as an eluent for column chromatography. ysical State: solid Colour: white Mp: 158 ºC R f = 0.44 in 1:9 EtAc/Hexane FTIR (KBr): 3059, 2925, 2837, 1730, 1598, 1495, 1374, 1154, 1093 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 5H), (m, 4H), (m, 3H), (m, 2H), (m, 3H), 6.39 (m, 1H), (m, 1H), 4.13 and 4.07 (AB q, 2H, J = 16.0 Hz), 3.61 (s, 2H), 3.60 (s, 3H), 2.38 (s, 3H), 2.28 (s, 3H), 1.81 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.4, 153.8, 149.0, , 144.9, 142.0, 136.8, 136.1, 136.0, 133.4, 129.7, 129.5, 129.4, 129.1, 128.7, , 126.5, 121.4, 112.7, 111.4, 107.9, 96.4, 87.9, 59.1, 55.8, 52.3, 51.8, 24.5, 21.9, HRMS: calcd. for C 39 H 37 N 6 S+Na: ; found:

78 Indoline (3bc): According to the general procedure the product was isolated in 71% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: gummy liquid Colour: light green R f = 0.58 in 1:9 EtAc/Hexane FTIR (Neat): 3054, 2899, 2950, 1729, 1602, 1497, 1265, 1164, 1041 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.30 (d, 2H, J = 7.9 Hz), (m, 4H), (m, 1H), (m, 2H), (m, 2H), (m, 3H), 6.51 (d, 1H, J = 2.5 Hz), 6.22 (d, 1H, J = 8.4 Hz), 4.27 (s, 2H), 3.71 (s, 3H), 3.70 (s, 3H), 2.37 (s, 3H), 1.93 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.5, (d, J = Hz), 153.5, 145.3, (d, J = 3.3 Hz), 137.1, 136.8, (d, J = 14.6 Hz), (d, J = 7.9 Hz), 129.3, 127.9, 127.6, 127.5, 126.4, 113.7, 113.5, 112.5, 111.2, 107.8, 88.3, 58.4, 55.9, 52.2, 51.7, 24.6, HRMS: calcd. for C 32 H 30 N 3 F+H: ; found:

79 Indoline (3bd): According to the general procedure the product was isolated in 78% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: gummy solid Colour: colourless R f = 0.60 in 1:9 EtAc/Hexane FTIR (Neat): 3052, 2983, 1728, 1600, 1531, 1493, 1348, 1265, 1102, 1040 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ (m, 2H), (m, 2H), (m, 5H), (m, 4H), (m, 1H), (m, 1H), (m, 1H), 4.29 (m, 2H), 3.71 (s, 3H), 3.71 (s, 3H), 2.38 (s, 3H), 2.04 (s, 3H), 1.97 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.6, 153.4, 145.4, 142.2, 137.3, 136.9, 136.6, 136.3, 135.9, 130.6, 129.2, 129.0, 127.9, 127.3, 126.8, 126.4, 126.2, 125.0, 112.3, 114.1, 107.6, 88.3, 58.7, 55.9, 52.1, 51.6, 24.2, 21.4, HRMS: calcd. for C 33 H 33 N 3 +H: ; found:

80 Indoline (3be): According to the general procedure the product was isolated in 52% yield using the mixture of ethyl acetate/hexanes (2:98) as an eluent for column chromatography. ysical State: solid Colour: colourless Mp: 94 ºC R f = 0.59 in 1:9 EtAc/Hexane FTIR (KBr): 3061, 3028, 2926, 2854, 1738, 1603, 1485, 1257, 1125 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 7.54 (m, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 1H), (m, 3H), (m, 2H), 6.63 (dd, 1H, J = 2.5, 5.9 Hz), 6.53 (d, 1H, J = 2.5 Hz), 6.25 (d, 1H, J = 8.4 Hz), 4.24 and 4.16 (AB q, 2H, J = 16.5 Hz), 3.72 (s, 3H), 3.69 (s, 3H), 2.36 (s, 3H), 1.93 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.4, 153.8, 145.4, 142.0, 138.1, 137.0, 136.3, 135.6, 131.3, (q, J = 31.7 Hz), 129.4, 126.5, 127.7, 127.2, 126.5, 126.3, (q, J = 3.6 Hz), (q, J = Hz), (q, J = 3.6 Hz), 112.6, 111.0, 108.2, 88.1, 58.8, 55.9, 52.0, 52.0(2), 23.6, HRMS: calcd. for C 33 H 30 N 3 F 3 +H: ; found:

81 Indoline (3bf): According to the general procedure the product was isolated in 50% yield using the mixture of ethyl acetate/hexanes (3:97) as an eluent for column chromatography. ysical State: solid Colour: yellow Mp: 166 ºC R f = 0.49 in 1:9 EtAc/Hexane FTIR (KBr): 3056, 2940, 2847, 1728, 1599, 1496, 1330, 1265, 1040, 1016 cm 1. 1 H NMR (400 MHz, CDCl 3, 24 C): δ 8.25 (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 3H), (m, 2H), (m, 1H), 6.55 (m, 1H), 6.29 (d, 1H, J = 8.4 Hz), 4.25 and 4.15 (AB q, 2H, J = 16.4 Hz), 3.76 (s, 3H), 3.70 (s, 3H), 2.38 (s, 3H), 1.96 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C): δ 171.2, 154.0, 147.5, 145.3, 141.9, 139.4, 136.8, 136.5, 135.2, 134.2, 129.5, 128.5, 128.1, 127.4, 126.7, 126.3, 123.9, 122.1, 112.7, 110.9, 108.5, 87.9, 58.9, 55.8, 52.2, 52.1, 23.4, HRMS: calcd. for C 32 H 30 N 2 5 +H: ; found:

82 22. Deuterium exchange experiment: 2-Vinyl anilines 1b (0.15 mmol, 1 equiv.), [Pd(cinnamyl)Cl] 2 ( mmol, 6mol%), D 2 (0.001 ml, 1 equiv) and toluene (1.5 ml) were added under argon atmosphere to an over dried 10 ml reaction tube equipped with stir bar. The reaction tube was sealed and kept at 120 C in pre-heated oil bath. Subsequently, the solution of diazo esters 2a (0.36 mmol, 2 equiv) in toluene (0.1 ml) was introduced slowly through syringe pump (addition rate = ml/min). After the TLC analysis, it was cooled to room temperature and solvent was removed under reduced pressure. Purification of the resultant crude through column chromatography using hexane/ethyl acetate mixture as eluent afforded the mixture of indoline and deuterated indoline derivatives in 1: 0.3 ratio (81% yield). In another experiment, the reaction was stopped after 1h. Both product and starting material were isolated. Although similar deuterium incorporation was observed in the product, no deuterium incorporation was observed in the recovered starting material. 82

83 H NMR (400 MHz, CDCl 3, 24 C) N CH2 D CMe 2.00 ppm NAME spa41015 EXPN 252 Date_ Time PULPRG zg30 TD NS 16 DS 2 SWH Hz FIDRES Hz AQ sec RG DW usec TE K D sec NUC1 1H P usec PLW W SF MHz SI SF MHz WDW EM LB 0.30 Hz PC ppm 13 C{ 1 H} NMR (100 MHz, CDCl 3, 24 C NAME spa41015 EXPN 255 N CH2 D CMe ppm Date_ Time PULPRG zgpg30 TD NS 256 DS 4 SWH Hz FIDRES Hz AQ sec RG DW usec TE K D sec d sec DELTA sec SF MHz NUC1 13C P usec PLW W SF MHz NUC2 1H CPDPRG[2 waltz16 PCPD usec PLW W PLW W PLW W SI SF MHz WDW EM LB 1.00 Hz PC ppm 83

84 23. HPLC Spectra for Compound (3b): 84

85 24. Crystallographic data and structure refinements summary for compound 3m. DATA 3m Molecular Structure (rtep Structure) CCDC number Formula C 31 H 28 FN 2 Formula weight Color Colorless Temperature/K 296(2) Radiation Mo K Wavelength/Å Crystal system Monoclinic Space group P 21/c a (Å) (5) b (Å) (14) c (Å) (7) ( ) 90 ( ) (2) ( ) 90 Volume (Å 3 ) (2) Z 4 Density (g/ml) (1/mm) F (000) 984 (min, max) 2.02, 25 No. of unique reflns 4312 No. of parameters 319 R_obs, wr 2 _obs , min, max (eå -3 ) 0.3, GooF

86 25. Crystallographic data and structure refinements summary for compound 3aq. DATA 3aq Molecular Structure (rtep Structure) CCDC number Formula C 28 H 29 N 1 2 Formula weight Color Yellow Temperature/K 296(2) Radiation Mo K Wavelength/Å Crystal system Monoclinic Space group P 21/n a (Å) (2) b (Å) (4) c (Å) (4) ( ) 90 ( ) (10) ( ) 90 Volume (Å 3 ) (10) Z 4 Density (g/ml) 1.19 (1/mm) F (000) 884 (min, max) 1.902, No. of unique reflns 4528 No. of parameters 301 R_obs, wr 2 _obs , min, max (eå -3 ) 0.211, GooF

87 26. Computational Results Computational Methods: The complete geometrical optimization of all structures and transition states (TSs) were carried out using Density Functional Theory (DFT) based B3LYP 4 method employing effective core potential basis set LANL2DZ 5 for Pd and 6-31G(d) 6 basis set for rest of the atoms. B3LYP method is believed to be reliable for Pd based complexs. 7-9 Solvent (Toluene) effects were included with polarizable continuum model (PCM). All the calculations were performed using Gaussian 09 suite of programs. 10 All the gas-phase-optimized geometries were verified as minima or first-order saddle points by the frequency calculations as well as for the Zero Point Energy (ZPE), Enthalpy and Gibbs energy corrections at 298 K and 1 atm. As in the standard practice, the presence of one imaginary frequency criteria was used for the characterization of TSs. Further, the transition states were also verified by the intrinsic reaction coordinate (IRC) calculations. 11 DFT Studies on the formation of N-ylide B: The energy profiles and all the optimized geometries are depicted in Figure S1 and Figure S2. As discussed in Scheme 3 (see manuscript), in pathway X palladium catalyst interacts with diazo compound 2 to give diazo compound palladium intermediate ([Pd]+2 INT ). Then N 2 is released via transition state TS [Pd]+2 affording palladium carbenoid A. The addition of ortho-vinyl aniline 1 to A forms an intermediate A1 through TS A1 which is further isomerizes into N-ylide B via transition state TS A1B (Figure S1). Pathway Y is initialized with the reaction of ortho-vinyl aniline 1 with palladium catalyst which is followed by the addition of reagent 2 leads to the intermediate A1 through the formation of intermediate E+2 INT and the release of N 2 via transition state TS E+2. Then the similar sequence of reactions is followed as carried out in Pathway X to result N-ylide B. The overall activation barriers for both the pathways are and kcal/mol respectively. The energy values of 87

88 G kcal/mol all the TSs are listed in Table S3. Based on these results, pathway X is a more favorable reaction sequence than pathway Y. This is may be due to the steric bulk of the reagents in pathway Y while reacting 2 with the intermediate of palladium complex E having ortho-vinyl aniline moiety. TS [Pd] TS E [Pd]+2a INT 7.21 E+2 INT [Pd]+2a [Pd]+1 TS [Pd] E 3.03 E A A TS A A TS A1B B Figure S1: Energy profile diagram for the formation of N-ylide B through pathways X and Y. Color indication, pathway X is in green, Y is in red and black are common steps in both the pathways DFT Studies on the Cyclization of N-ylide B. Two possible reaction paths were proposed for the formation of cyclization of N-ylide B into indoline 3. ne is metallo-ene kind of reaction and the other is Heck-type of cyclization. Figure S2 presents the free energy profiles calculated for the two possible pathways proposed. Heck type of cyclisation reactions are initiated from N-ylide B and the metallo-ene reactions are initiated from intermediate C. As the energy difference between B and C is very low (3.92 kcal/mol), N-ylide B isomerizes to intermediate C rapidly from which metallo-ene type of reaction is initiated. Metallo-ene reactions of C, proceed through 88

89 six membered ring transition states of both chair-like and boat-like conformations ch and bt ) where both of them predominantly result to both phenyl group () in same side, which in turn afford the excellent cis-diastereoselectivity. TS@E ch has low activation barrier compare to TS@E bt, which is possibly due to the formation of stable chair-like conformation of six-membered transition state. n the other hand, transition states TS 5ExT and TS 6EnT are associated with Heck type reaction with 5-exo-trig and 6-endo-trig mode of cyclisation reactions, respectively. The activation barriers for the Heck type of reactions ( 30 kcal/mol) are high compared to the metallo-ene reactions (in the range of kcal/mol). This may be due to the steric repulsions between phenyl ring and allene-type group of Pd complex during the Heck-type of cyclisation which is evident from TS 5EXT.The metallo-ene type reactions and Heck type reaction under 5-exo-trig cyclization yielded the zwitterion D through various reaction pathways associated with corresponding TSs. n the other hand, Heck-type reaction under 6-endo-trig cyclization affords 6-membered ring product 5 through E 6EnT, which is not observed in the present transformation. 89

90 Figure S2 Energy profile diagram for the cyclization of N-ylide B to indoline. [Pd]+2a INT TS [Pd]+2 90

91 A TS A1 TS A1B TS [Pd]+1 E+2 INT TS E+2 91

92 ch bt TS 5ExT TS 6EnT Figure S3 ptimized geometries of Transition states and intermediates involved in the reaction sequences. Table S3 Activation of Gibbs Free Energies (in kcal/mol), Enthalpies (in kcal/mol) and energies (in kcal/mol) of stationary points. TS G G E E H H Charge on Pd TS [Pd] TS A TS A1B