Modular Synthesis of Naphtho-Thiophenes by Pd- Catalyzed Tandem Direct-Arylation/Suzuki- Coupling

Transcription

1 Modular Synthesis of Naphtho-Thiophenes by Pd- Catalyzed Tandem Direct-Arylation/Suzuki- Coupling Norman Nicolaus, Patrick T. Franke and Mark Lautens* [*]Davenport Chemical Laboratories Department of Chemistry, University of Toronto 80 St. George St. Toronto, Ontario, M5S 3H6 Fax (416) Contents 1. General Methods S2 2. General Procedure for Suzuki-Miyaura Coupling S3 3. General Procedure for Olefination S3 4. General Procedure for Pd-Catalyzed Tandem Direct-Arylation/Suzuki-Coupling S4 5. Characterization of Compounds S5 6. Crystal structure S20 7. Spectra S21 S1

2 1. General Methods General Experimental Procedures: Unless otherwise noted, reactions were carried out under argon atmosphere, in sealed tubes (2-5 or ml glass tubes with sealable cap and Teflon septa provided by Biotage) with magnetic stirring. Organic solutions were concentrated by rotary evaporation at C under 40 Torr (house vacuum). Analytical thin layer chromatography (TLC) was carried out on precoated SIL G/UV254 (0.2 mm) plates from EM Seperations. Visualization was done under a 254 nm UV light source and generally by immersion in acidic aqueous-ethanolic vanillin solution, or in potassium permanganate (KMnO 4 ), followed by heating using a heat gun. Purification of reaction products was generally done by flash chromatography with Silicycle Ultra-Pure mesh silica gel. Materials: Dioxane was distilled under nitrogen from Na/benzophenone immediately prior to use. All reagents and metal catalysts were purchased from Sigma-Aldrich, Lancaster, Alfa Aesar or Strem-Chemical Company and used without further purification unless otherwise noted. Instrumentalization: Melting points were recorded using a Fisher Johns melting point apparatus and are uncorrected. 1 H and 13 C NMR spectra were recorded at room temperature using a Varian Gemini-300, Unity-400 or Mercury 400 machine. Chemical shifts ( ) are reported in ppm relative to residual solvent signals (CDCl 3, 7.24 ppm for 1 H NMR, CDCl 3, 77.0 ppm for 13 C NMR). The following abbreviations are used to indicate the multiplicity in NMR spectra: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet. IR spectra were obtained using a Nicolet DX FT IR spectrometer in CHCl 3 as thin films on NaCl plates. High resolution mass spectra were obtained from a SI2 Micromass 70S- 250 mass spectrometer (EI) or an ABI/Sciex Qstar mass spectrometer (ESI). S2

3 2. General Procedure for Suzuki-Miyaura Coupling for the Synthesis of 6 The procedure was adapted from literature. 1 An oven dried Biotage microwave round-bottom flask with a stirrer bar was cooled under argon. Pd 2 (dba) 3 (0.5 mol %), S-Phos (2 mol %), K 3 PO 4 (2 equiv) and the boronic acid (2 equiv) were transferred into the flask. The flask was purged with argon for ~15 minutes. Toluene (1 M) was added to the flask, then the arylbromide (1 equiv) was added via syringe and more toluene (1 M) was used to rinse the arylbromide vial. The flask was capped by a Teflon microwave cap and the reaction was heated to 100 C and the reaction was stirred overnight. The crude mixture was filtered through a plug of celite, concentrated under reduced pressure, and purified by flash chromatography. 3. General Procedure for Olefination PPh 3 (15 mmol, 3.0 equiv) was placed in an oven-dried round-bottomed flask which was flushed with argon. CH 2 Cl 2 (50 ml) was added as solvent and the reaction mixture was cooled down to 0 C before CBr 4 (15.0 mmol, 3.0 equiv) was added. The reaction was stirred for 15 min while the mixture turned orange due to the formation of Br 2. Then the aldehyde (5 mmol, 1.0 equiv) was added and the mixture was allowed to warm up to rt and stirred for 14 h. For purification the mixture was filtered over silica gel and eluted with 10 % ethyl acetate in pentane. The volume of the solution was reduced and the remaining crude product was further purified by column chromatography. 1 Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, S3

4 4. General Procedure for Pd-Catalyzed Tandem Direct- Arylation/Suzuki-Coupling An oven-dried Biotage microwave vial, capped with a septum, was cooled under argon. gem-dibromoolefin (0.1 mmol), Pd(OAc) 2 (10 mol %), tricyclohexylphosphine (20 mol %), Cs 2 CO 3 (2.0 equiv), CsOPiv (50 mol %), tetrabutylammonium bromide (1.0 equiv) and phenylboronic acids (1.5 equiv) were transferred into the flask and purged with argon for ~15 minutes. Dioxane (2.5 ml) was added and the septum subsequently was replaced by a Teflon microwave cap. The vial was heated in an oil bath to 100 C for 16 h and after cooling down to room temperature, the mixture was filtered over Celite and washed with DCM. The solution was concentrated and purified by column chromatography over silica gel. S4

5 5. Characterization of Compounds 11 2-(thiophen-3-yl)benzaldehyde Following the general procedure 2 the product 11 was isolated by FC on silica (EtOAc/pentane 1:10) in >97% yield as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), (m, 1H), (m, 1H), (m, 3H), 7.27 (dd, J = 3.0, 1.3 Hz, 1H), 7.17 (dd, J = 4.9, 1.3 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 192.3, 140.4, 138.3, 134.0, 133.6, 130.5, 129.3, 127.8, 127.5, 126.2, HRMS (ESI+) calculated for [M+H] + : [C 11 H 9 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3098 (m), 2921 (w), 2861 (m), 2755 (m), 1684 (s), 1653 (m), 1597 (s), 1474 (m), 1363 (m), 1270 (m), 1243 (m), 1198 (m), 860 (m), 829 (m), 794 (m), 759 (m), 668 (s) (2-(2,2-dibromovinyl)phenyl)thiophene Following the general procedure 3 the product 12 was isolated by FC on silica (EtOAc/pentane 1:40 to 1:10) in 70% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 2H), (m, 2H), 7.28 (dd, J = 3.0, 1.3 Hz, 1H), 7.18 (dd, J = 5.0, 1.3 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.5, 137.6, 135.5, 133.7, 129.4, 129.4, 128.7, 128.7, 127.1, 125.5, 123.9, HRMS (ESI+) calculated for [M+H] + : [C 12 H 9 Br 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3103 (w), 3060 (w),3025 (w), 2923 (m), 2852 (w), 1599 (w), 1479 (m), 1445 (m), 1247 (w), 1190 (w), 1105 (w), 1083 (w), 950 (w), 889 (m), 859 (s), 823 (m), 791 (s), 752 (s). S5

6 13 2-(4-methylthiophen-3-yl)benzaldehyde Following the general procedure 2 the product 13 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10) in 91% yield as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ 9.85 (d, J = 0.7 Hz, 1H), 8.02 (dd, J = 7.8, 1.2 Hz, 1H), 7.64 (ddd, J = 13.2, 6.5, 2.7 Hz, 1H), (m, 1H), 7.35 (dd, J = 7.6, 0.8 Hz, 1H), 7.18 (d, J = 3.2 Hz, 1H), (m, 1H), 2.08 (d, J = 0.8 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 192.3, 140.9, 138.6, 137.0, 134.6, 133.6, 131.1, 128.0, 127.2, 125.2, 122.0, HRMS (ESI+) calculated for [M+H] + : [C 12 H 11 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3097 (m), 3060 (w), 2920 (m), 2849 (m), 2746 (m), 1693 (s), 1646 (m), 1597 (s), 1487 (m), 1456 (m), 1446 (m), 1437 (m), 1269 (m), 1230 (m), 1195 (m), 863 (m), 825 (m) (2-(2,2-dibromovinyl)phenyl)-4-methylthiophene Following the general procedure 3 the product 14 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20) in 82% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 1H), 7.13 (s, 1H), 7.11 (d, J = 3.2 Hz, 1H), (m, 1H), 2.07 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.9, 137.1, 136.7, 136.5, 134.9, 130.3, 128.7, 128.3, 127.3, 124.1, 121.6, 90.4, HRMS (ESI+) calculated for [M+H] + : [C 13 H 11 Br 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3096 (w), 3060 (w), 3023 (w), 2919 (m), 2857 (w), 1895 (w), 1852 (w), 1740 (w), 1704 (m), 1653 (m), 1638 (w), 1559 (m), 1506 (m), 1471 (w), 1423 (w), 888 (w), 859 (m), 797 (m), 668 (s). S6

7 15 2-(5-methylthiophen-3-yl)benzaldehyde Following the general procedure 2 the product 15 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10) in >97% yield as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), (m, 1H), (m, 1H), 7.44 (d, J = 7.9 Hz, 2H), 7.01 (d, J = 1.5 Hz, 1H), (m, 1H), 2.53 (d, J = 1.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 192.6, 140.8, 140.7, 138.1, 133.9, 133.6, 130.4, 127.6, 127.6, 127.5, 122.9, HRMS (ESI+) calculated for [M+H] + : [C 12 H 11 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3096 (w), 3064 (w), 2950 (m), 2920 (m), 2858 (m), 2752 (w), 1700 (s), 1597 (m), 1490 (m), 1268 (m), 1229 (m), 1195 (m), 835 (w), 769 (m), 751 (m) (2-(2,2-dibromovinyl)phenyl)-2-methylthiophene Following the general procedure 3 the product 16 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20) in 95% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 3H), 7.02 (d, J = 1.5 Hz, 1H), (m, 1H), 2.54 (d, J = 1.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.3, 139.9, 137.8, 135.9, 133.6, 129.3, 129.2, 128.6, 127.0, 126.9, 121.9, 90.6, HRMS (ESI+) calculated for [M+H] + : [C 13 H 11 Br 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3096 (w), 3060 (w), 2919 (m), 2855 (w), 1844 (w), 1800 (w), 1776 (w), 1700 (m), 1653 (m), 1576 (m), 1559 (m), 1506 (m), 1457 (w), 1440 (w), 1420 (w). S7

8 methoxy-2-(thiophen-3-yl)benzaldehyde Following the general procedure 2 the product 17 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:1 to 1:3) in >97% yield as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 7.46 (d, J = 2.8 Hz, 1H), 7.42 (dd, J = 4.9, 3.0 Hz, 1H), 7.38 (d, J = 8.5 Hz, 1H), 7.21 (dd, J = 3.0, 1.3 Hz, 1H), 7.17 (dd, J = 8.5, 2.9 Hz, 1H), 7.14 (dd, J = 4.9, 1.3 Hz, 1H), 3.88 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 192.3, 159.2, 138.0, 134.8, 133.6, 131.9, 129.4, 126.1, 124.6, 121.6, 109.8, HRMS (ESI+) calculated for [M+H] + : [C 12 H 11 O 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3105 (w), 3010 (w), 2956 (w), 2850 (w), 2743 (w), 1687 (s), 1603 (m), 1488 (m), 1390 (w), 1311 (w), 1278 (w), 1223 (w), 1190 (m), 1163 (w), 1045 (w), 1022 (w), 787 (m) (2-(2,2-dibromovinyl)-4-methoxyphenyl)thiophene Following the general procedure 3 the product 18 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:15 to 1:8) in 63% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.31 (s, 1H), (m, 2H), 7.12 (dd, J = 5.0, 1.3 Hz, 1H), 6.92 (dd, J = 8.5, 2.7 Hz, 1H), 3.84 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.4, 140.2, 137.5, 134.7, 130.5, 128.8, 128.3, 125.4, 123.1, 114.6, 114.3, 91.1, HRMS (ESI+) calculated for [M+H] + : [C 13 H 11 Br 2 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3106 (w), 3006 (w), 2956 (m), 2935 (m), 2902 (w), 2834 (w), 1606 (m), 1484 (m), 1307 (m), 1283 (m), 1237 (m), 1194 (m), 1165 (m), 1117 (w), 1052 (m), 1022 (w), 944 (m), 874 (m), 833 (m), 663 (s). S8

9 19 2-(benzo[b]thiophen-3-yl)benzaldehyde Following the general procedure 2 the product 19 was isolated by FC on silica (EtOAc/pentane 1:20) in >97% yield as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ 9.86 (d, J = 0.6 Hz, 1H), 8.09 (dd, J = 7.8, 1.1 Hz, 1H), 7.93 (dd, J = 7.2, 1.3 Hz, 1H), 7.68 (td, J = 7.5, 1.4 Hz, 1H), (m, 3H), (m, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 191.9, 139.9, 139.3, 139.3, 134.9, 133.9, 133.4, 131.3, 128.4, 127.6, 126.4, 124.9, 122.8, HRMS (ESI+) calculated for [M+NH 4 ] + : [C 15 H 14 N 1 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3083 (m), 3060 (m), 2844 (m), 2750 (w), 1692 (s), 1597 (s), 1457 (w), 1425 (m), 1392 (m), 1343 (m), 1294 (w), 1269 (m), 1259 (m), 1212 (m), 1193 (m), 1061 (m), 941 (w), 822 (m), 767 (s), 736 (s) (2-(2,2-dibromovinyl)phenyl)benzo[b]thiophene Following the general procedure 3 the product 20 was isolated by FC on silica (EtOAc/pentane 1:60) in 80% yield as a colorless solid (mp = 64 C). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 1H), 7.16 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.0, 138.4, 136.9, 135.4, 135.1, 134.8, 130.4, 129.3, 128.5, 127.6, 125.6, 124.5, 124.3, 123.0, 122.7, HRMS (ESI+) calculated for [M+H] + : [C 16 H 11 Br 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3058 (m), 3024 (m), 1597 (m), 1574 (w), 1565 (m), 1556 (m), 1518 (m), 1475 (m), 1454 (m), 1441 (m), 1424 (m), 1341 (m), 1316 (m), 1275 (m), 1259 (s), 1217 (m), 1162 (m), 1145 (m), 1097 (m), 1057 (m), 1043 (m), 1020 (m), 953 (m), 942 (m), 907 (m), 889 (s), 860 (s), 787 (s). S9

10 21a 2-(benzo[b]thiophen-3-yl)thiophene-3-carbaldehyde Following the general procedure 2 the product 21a was isolated by FC on silica (EtOAc/pentane 1:20) as a mixture as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ 9.76 (s, 1H), (m, 1H), (m, 1H), 7.62 (d, J = 5.4 Hz, 1H), 7.58 (s, 1H), (m, 2H), 7.37 (dd, J =5.4, 0.8 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 185.4, 148.1, 140.0, 139.0, 138.3, 128.6, 126.6, 126.2, 125.9, 125.3, 125.2, 122.9, IR neat, ν (cm -1 ) 3092 (m), 2821 (m), 1687 (s), 1679 (s), 1668 (s), 1662 (s), 1511 (m), 1422 (m), 1402 (m), 1386 (m), 1234 (s), 1152 (m), 821 (m), 792 (m), 762 (m), 735 (m), 701 (m) (3-(2,2-dibromovinyl)thiophen-2-yl)benzo[b]thiophene Following the general procedure 3 the product 21 was isolated by FC on silica (hexane) in 30% yield over two steps as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), 7.83 (d, J = 5.4 Hz, 1H), (m, 1H), 7.46 (s, 1H), (m, 3H), 7.23 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.0, 138.2, 136.5, 133.8, 131.5, 128.5, 127.5, 126.9, 124.9, 124.8, 124.7, 123.1, 122.8, HRMS (ESI+) calculated for [M+H] + : [C 14 H 9 Br 2 S 2 ] ; found: IR neat, ν (cm -1 ) 3373 (m), 3093 (m), 3061 (w), 1703 (w), 1434 (m), 1215 (s), 1191 (s), 1182 (s), 836 (m), 816 (s), 758 (s), 732 (m), 702 (m), 683 (m), 652 (w). S10

11 23 4-(4-methoxyphenyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 23 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:1) in 66% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.33 (d, J = 8.1 Hz, 1H), 8.05 (d, J = 5.5 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), (m, 2H), 7.69 (s, 1H), (m, 3H), (m, 2H), 3.89 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 159.6, 137.8, 136.5, 134.7, 133.1, 131.9, 129.6, 128.5, 128.4, 126.2, 126.2, 125.6, 124.0, 123.5, 122.4, 114.2, HRMS (ESI+) calculated for [M+H] + : [C 19 H 15 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3052 (w), 2930 (m), 2834 (m), 1608 (m), 1515 (m), 1498 (m), 1359 (m), 1286 (m), 1248 (m), 1178 (m), 1033 (m), 913 (m), 901 (m), 830 (m), 748 (s), 745 (s), 732 (m), 719 (m) phenylnaphtho[2,1-b]thiophene Following the general procedure 4 the product 24 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 70% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.35 (d, J = 8.1 Hz, 1H), 8.06 (d, J = 5.5 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H), (m, 2H), 7.74 (s, 1H), (m, 2H), (m, 3H), (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.6, 137.5, 136.6, 135.1, 131.8, 128.8, 128.6, 128.6, 128.4, 128.1, 126.4, 126.3, 125.6, 124.4, 123.5, HRMS (ESI+) calculated for [M+H] + : [C 18 H 13 S 1 ] ; found: IR neat, ν (cm -1 ) 3056 (m), 2923 (m), 1704 (w), 1493 (s), 1357 (m), 1150 (m), 884 (m), 763 (s), 748 (s), 720 (s), 699 (s), 692 (m). S11

12 25 4-(p-tolyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 25 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:15 to 1:8) in 71% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 (d, J = 8.1 Hz, 1H), 8.08 (d, J = 5.5 Hz, 1H), 7.98 (d, J = 7.8 Hz, 1H), 7.74 (d, J = 4.7 Hz, 2H), 7.71 (s, 1H), (m, 2H), (m, 1H), 7.36 (d, J = 7.8 Hz, 2H), 2.48 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 138.0, 137.7, 137.6, 136.5, 135.0, 131.8, 129.5, 128.6, 128.5, 128.3, 126.2, 125.6, 124.2, 123.5, 122.3, HRMS (ESI+) calculated for [M+H] + : [C 19 H 15 S 1 ] ; found: IR neat, ν (cm -1 ) 3056 (w), 3023 (w), 2921 (m), 2852 (w), 1734 (w), 1704 (w), 1680 (w), 1653 (w), 1616 (w), 1498 (w), 1359 (w), 1184 (w), 1160 (w), 1133 (w), 1113 (w), 1091 (w), 900 (w), 884 (w) 817 (m) (4-chlorophenyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 26 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 61% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.34 (d, J = 8.2 Hz, 1H), 8.06 (d, J = 5.5 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 2H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.0, 137.1, 136.7, 134.1, 133.8, 131.7, 129.7, 129.0, 128.6, 126.6, 126.3, 125.8, 124.5, 123.6, HRMS (TOF EI+) calculated for [M] + : [C 18 H 11 S 1 Cl 1 ] ; found: IR neat, ν (cm -1 ) 3060 (m), 2924 (m), 1492 (s), 1358 (m), 1162 (m), 1149 (m), 1134 (m), 1090 (s), 1014 (m), 913 (w), 885 (m), 827 (s), 748 (s), 725 (s), 715 (s). S12

13 27 4-(4-fluorophenyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 27 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:5) in 60% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.39 (d, J = 8.2 Hz, 1H), 8.11 (d, J = 5.5 Hz, 1H), 8.01 (d, J = 7.9 Hz, 1H), (m, 2H), 7.74 (s, 1H), (m, 2H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ (d, J = Hz), (d, J = 79.6 Hz), (d, J = 3.3 Hz), 134.0, 131.7, 130.2, 130.1, 128.6, 128.5, 126.5, 126.3, 125.7, 124.4, 124.3, 123.6, 122.5, 115.8, HRMS (ESI+) calculated for [M+H] + : [C 18 H 12 F 1 S 1 ] ; found: IR neat, ν (cm -1 ) 2957 (w), 2922 (s), 2851 (m), 1603 (m), 1511 (s), 1498 (s), 1358 (m), 1222 (m), 1157 (m), 1092 (w), 1016 (w), 901 (w), 884 (w), 832 (m) (p-tolyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 28 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10 to 1:1) in 65% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.35 (d, J = 8.2 Hz, 1H), 8.07 (d, J = 5.5 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), (m, 2H), (m, 2H), 7.73 (s, 1H), (m, 2H), (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.1, 137.1, 136.4, 133.0, 132.6, 131.5, 129.1, 128.9, 128.8, 127.1, 126.4, 126.0, 125.0, 123.6, 122.6, 118.8, HRMS (ESI+) calculated for [M] + : [C 19 H 11 N 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3103 (m), 3062 (m), 2923 (m), 2853 (m), 2228 (s), 1606 (s), 1511 (w), 1497 (m), 1417 (w), 1357 (m), 1160 (w), 1149 (w), 1114 (w), 1095 (w), 901 (m), 885 (w) 834 (m). S13

14 29 4-(naphtho[2,1-b]thiophen-4-yl)benzaldehyde Following the general procedure 4 the product 29 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 63% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.35 (d, J = 8.2 Hz, 1H), 8.07 (d, J = 5.5 Hz, 1H), (m, 2H), (m, 3H), 7.77 (s, 1H), (m, 2H), (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 191.7, 146.5, 136.8, 136.5, 135.7, 133.5, 131.4, 130.1, 128.9, 128.8, 128.7, 126.9, 126.3, 125.8, 124.9, 123.5, HRMS (ESI+) calculated for [M+H] + : [C 19 H 13 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3060 (m), 2824 (m), 1696 (s), 1664 (w), 1605 (s), 1581 (m), 1560 (m), 1497 (m), 1357 (m), 1307 (m), 1207 (m), 1170 (m), 1150 (m), 1132 (m), 902 (m), 830 (s), 751 (m), 731 (m), 720 (m). 30 methyl 4-(naphtho[2,1-b]thiophen-4-yl)benzoate Following the general procedure 4 the product 30 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10 to 1:1) in 81% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.34 (d, J = 8.2 Hz, 1H), (m, 2H), 8.06 (d, J = 5.5 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), (m, 2H), 7.76 (s, 1H), (m, 2H), (m, 1H), 3.96 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 166.9, 145.1, 136.9, 136.8, 133.9, 131.6, 130.1, 129.7, 128.8, 128.7, 128.4, 126.8, 126.4, 125.8, 124.8, 123.6, 122.4, HRMS (ESI+) calculated for [M+H] + : [C 20 H 15 O 2 S 1 ] ; found: IR neat, ν (cm -1 ) 2950 (m), 2923 (m), 2850 (m), 1720 (s), 1609 (m), 1434 (m), 1415 (w), 1357 (m), 1311 (m), 1285 (s), 1191 (w), 1180 (w), 1151 (w), 1113 (m), 1104 (m), 1018 (m), 903 (w), 846 (w), 773 (m), 722 (m). S14

15 31 4-(4-methyl-3-nitrophenyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 31 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:4 to 1:1) in 63% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.40 (d, J = 1.8 Hz, 1H), 8.34 (d, J = 8.2 Hz, 1H), 8.07 (d, J = 5.5 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.94 (dd, J = 7.9, 1.8 Hz, 1H), 7.74 (s, 1H), (m, 2H), (m, 1H), 7.49 (d, J = 7.9 Hz, 1H), 2.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 149.5, 139.6, , 136.6, 133.3, 133.2, 132.7, 132.4, 131.6, 128.9, 128.8, 127.0, 126.4, 125.9, 124.8, 124.5, 123.6, 122.6, HRMS (ESI+) calculated for [M+H] + : [C 19 H 14 N 1 O 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3111 (m), 2960 (m), 2927 (m), 2854 (m), 1695 (w), 1653 (w), 1495 (m), 1481 (s), 1456 (w), 1448 (w), 1436 (w), 1378 (m), 1338 (s), 1281 (m), 1162 (m), 1134 (m), 1032 (m), 972 (w), 904 (m) (thiophen-2-yl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 32 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 67% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.33 (d, J = 8.1 Hz, 1H), 8.05 (d, J = 5.5 Hz, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.84 (s, 1H), 7.80 (dd, J = 2.9, 1.3 Hz, 1H), 7.61 (dd, J = 8.0, 3.1 Hz, 2H), (m, 2H), 7.49 (dd, J = 5.0, 2.9 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 141.0, 137.0, 136.7, 131.6, 129.6, 128.5, 127.7, 126.4, 126.1, 126.1, 125.7, 123.9, 123.5, 122.9, HRMS (ESI+) calculated for [M+H] + : [C 16 H 11 S 2 ] ; found: IR neat, ν (cm -1 ) 3103 (m), 1700 (w), 1579 (m), 1561 (m), 1496 (m), 1404 (m), 1371 (m), 1340 (m), 1145 (m), 901 (m), 882 (m), 866 (m), 850 (m), 840 (s), 789 (s), 780 (s), 748 (s). S15

16 33 4-(2-(methoxymethyl)phenyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 33 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:5 to 1:1) in 59% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.37 (d, J = 8.2 Hz, 1H), 8.05 (d, J = 5.4 Hz, 1H), 7.95 (d, J = 7.7 Hz, 1H), (m, 3H), (m, 2H), (m, 3H), 4.29 (s, 2H), 3.21 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 139.2, , 136.5, 136.0, 133.3, 131.4, 129.7, 128.6, 128.6, 128.6, 128.5, 127.6, 126.6, 126.4, 125.6, 125.0, 123.6, 122.3, 72.0, HRMS (ESI+) calculated for [M+NH 4 ] + : [C 20 H 20 N 1 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3102 (w), 3059 (m), 2981 (m), 2923 (s), 2889 (m), 2872 (m), 1490 (m), 1448 (m), 1436 (w), 1381 (m), 1357 (s), 1237 (w), 1193 (m), 1112 (s), 1092 (s), 1067 (w), 968 (m), 947 (m), 936 (w) methoxy-4-(p-tolyl)naphtho[2,1-b]thiophene Following the general procedure 4 the product 34 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:1) in 62% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.26 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 5.5 Hz, 1H), 7.72 (d, J = 8.0 Hz, 2H), 7.67 (s, 1H), 7.60 (d, J = 5.5 Hz, 1H), 7.34 (dd, J = 10.0, 5.3 Hz, 3H), 7.27 (dd, J = 8.7, 2.7 Hz, 1H), 3.97 (s, 3H), 2.48 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 157.7, 138.2, 138.0, 136.9, 135.9, 135.8, 133.3, 129.7, 128.5, 126.6, 125.3, 123.8, 123.8, 122.3, 118.1, 107.7, 55.6, HRMS (TOF EI+) calculated for [M] + : [C 20 H 16 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3377 (w), 2930 (m), 1700 (w), 1623 (s), 1503 (s), 1230 (m), 1216 (m), 1194 (m), 1185 (m), 1172 (m), 913 (s), 817 (m), 743 (s), 724 (m), 598 (w). S16

17 35 2-ethoxy-5-(7-methoxynaphtho[2,1-b]thiophen-4-yl)pyridine Following the general procedure 4 the product 35 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10 to 2:1) in 71% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.56 (d, J = 2.1 Hz, 1H), 8.23 (d, J = 8.9 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), 6.87 (dd, J = 8.5, 0.4 Hz, 1H), 4.46 (q, J = 7.1 Hz, 2H), 3.95 (s, 3H), 1.46 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 163.7, 157.5, 146.3, 138.6, 136.8, 135.5, 133.0, 132.1, 129.4, 126.4, 125.1, 123.7, 123.6, 122.2, 118.2, 110.9, 107.5, 62.0, 55.4, HRMS (TOF EI+) calculated for [M] + : [C 20 H 17 N 1 O 2 S 1 ] ; found: IR neat, ν (cm -1 ) 2977 (m), 2932 (m), 1621 (s), 1603 (s), 1492 (m), 1474 (m), 1463 (m), 1413 (m), 1371 (m), 1359 (m), 1342 (m), 1303 (m), 1287 (m), 1230 (m), 1173 (m), 1038 (s), 719 (m) (4-(2-methylnaphtho[2,1-b]thiophen-4-yl)phenyl)ethanone Following the general procedure 4 the product 36 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20) in 91% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.25 (d, J = 8.3 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 2H), 7.58 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H), 7.51 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H), 2.67 (d, J = 1.1 Hz, 3H), 2.66 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 197.7, 145.4, 141.1, , 136.5, 136.0, 133.6, 131.6, 128.8, 128.7, 128.6, 128.6, 126.6, 125.6, 123.8, 123.6, 120.4, 26.7, HRMS (ESI+) calculated for [M+H] + : [C 21 H 17 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3056 (w), 2958 (m), 2923 (s), 2871 (m), 2856 (m), 1722 (m), 1718 (m), 1680 (s), 1605 (m), 1560 (w), 1358 (m), 1266 (s), 1135 (m), 1073 (m), 957 (m), 834 (m), 773 (m), 749 (m). S17

18 37 2-(2-methylnaphtho[2,1-b]thiophen-4-yl)furan Following the general procedure 4 the product 37 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 49% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.24 (d, J = 8.1 Hz, 1H), 8.06 (s, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.76 (s, 1H), 7.71 (d, J = 1.1 Hz, 1H), (m, 3H), 6.96 (dd, J = 1.7, 0.8 Hz, 1H), 2.72 (d, J = 1.0 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 143.3, 140.5, 140.2, 137.2, 135.6, 131.6, 128.4, 128.0, 126.0, 125.4, 125.2, 123.5, 122.2, 120.5, , HRMS (TOF EI+) calculated for [M] + : [C 17 H 12 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3146 (m), 2918 (m), 2851 (m), 1509 (m), 1436 (w), 1373 (w), 1159 (m), 1146 (w), 1075 (m), 1031 (m), 988 (w), 850 (w), 783 (s), 706 (m) ([1,1'-biphenyl]-2-yl)-1-methylnaphtho[2,1-b]thiophene Following the general procedure 4 the product 38 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:1) in 87% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.66 (d, J = 8.5 Hz, 1H), 7.79 (dd, J = 8.0, 1.0 Hz, 1H), (m, 1H), (m, 3H), (m, 2H), 7.41 (s, 1H), (m, 2H), 7.15 (s, 1H), (m, 3H), 2.89 (d, J = 0.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 141.4, 141.1, 140.9, 138.5, 134.8, 134.8, 133.6, 132.1, 130.8, 130.7, 129.7, 129.0, 128.9, 128.4, 127.7, 127.2, 126.6, 126.5, 125.7, 124.7, 123.3, 123.1, HRMS (ESI+) calculated for [M+H] + : [C 25 H 19 S 1 ] ; found: IR neat, ν (cm -1 ) 3056 (m), 3028 (m), 3020 (m), 2965 (m), 2951 (m), 2916 (m), 1495 (w), 1478 (s), 1447 (s), 1428 (m), 1343 (m), 1141 (m), 1009 (m), 931 (s), 760 (s), 744 (s), 731 (s), 689 (s). S18

19 39 trimethyl(3-(1-methylnaphtho[2,1-b]thiophen-4-yl)phenyl)silane Following the general procedure 4 the product 39 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20) in 61% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.76 (d, J = 8.4 Hz, 1H), (m, 1H), 7.98 (s, 1H), (m, 2H), (m, 2H), (m, 2H), 7.29 (s, 1H), 2.99 (d, J = 0.5 Hz, 3H), 0.36 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 141.0, 139.7, 139.7, 135.7, 135.2, 134.3, 133.5, 133.0, 132.5, 129.9, 129.0, 129.0, 128.1, 125.9, 125.0, 124.7, 123.4, 123.2, 20.1, HRMS (ESI+) calculated for [M+H] + : [C 22 H 23 S 1 Si 1 ] ; found: IR neat, ν (cm -1 ) 3078 (w), 3045 (m), 2954 (m), 2917 (m), 2893 (w), 2864 (w), 1448 (m), 1340 (w), 1248 (m), 1225 (s), 1111 (w), 942 (m), 882 (w), 863 (m), 851 (m), 838 (m) (4-methoxyphenyl)benzo[b]naphtho[1,2-d]thiophene Following the general procedure 4 the product 40 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:20 to 1:10) in 75% yield as a colorless solid (mp = 165 C). 1 H NMR (400 MHz, CDCl 3 ) δ 9.04 (d, J = 8.5 Hz, 1H), 8.89 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.82 (s, 1H), (m, 3H), 7.59 (td, J = 7.0, 3.5 Hz, 2H), 7.48 (t, J = 7.3 Hz, 1H), 7.07 (d, J = 8.7 Hz, 2H), 3.90 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 159.6, 139.9, 139.4, 137.0, 134.9, 132.9, 132.5, 129.8, 129.6, 129.6, 129.4, 126.9, 126.8, 125.2, 125.1, 124.8, 124.7, 123.1, 123.0, 114.1, HRMS (TOF EI+) calculated for [M] + : [C 23 H 16 O 1 S 1 ] ; found: IR neat, ν (cm -1 ) 3056 (w), 2957 (m), 2836 (m), 1609 (m), 1512 (s), 1462 (m), 1440 (m), 1345 (m), 1288 (s), 1177 (m), 1106 (w), 1031 (m), 974 (w), 829 (m), 747 (s), 724 (s). S19

20 41 6-phenylbenzo[b]naphtho[1,2-d]thiophene Following the general procedure 4 the product 41 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:10 to 1:1) in 71% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 9.05 (d, J = 8.5 Hz, 1H), 8.90 (d, J = 8.3 Hz, 1H), 8.05 (d, J = 7.9 Hz, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.86 (s, 1H), (m, 2H), 7.74 (ddd, J = 8.4, 7.0, 1.3 Hz, 1H), (m, 2H), (m, 2H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 140.4, 139.9, 139.1, 137.0, 135.3, 132.5, 129.8, 129.7, 129.5, 128.8, 128.7, 128.3, 127.2, 127.1, 125.3, 125.2, 124.8, 124.7, 123.1, HRMS (TOF EI+) calculated for [M] + : [C 22 H 14 S 1 ] ; found: IR neat, ν (cm -1 ) 3054 (m), 3028 (m), 2923 (m), 2852 (w), 1585 (m), 1493 (s), 1448 (m), 1438 (m), 1343 (m), 1137 (m), 1075 (w), 1022 (w), 909 (m), 785 (s), 763 (s) 700 (s). 42a 2-(1-tosyl-1H-indol-3-yl)benzaldehyde Following the general procedure 4 the product 42a was isolated by FC on silica (EtOAc/pentane 1:6) in 36% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 9.83 (d, J = 0.6 Hz, 1H), (m, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.60 (td, J = 7.5, 1.4 Hz, 1H), 7.56 (s, 1H), (m, 2H), (m, 2H), (m, 3H), 2.29 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 191.7, 145.4, 136.0, 135.0, 134.8, 134.5, 134.0, 131.3, 130.8, 130.1, 128.4, 127.9, 126.9, 125.5, 125.4, 124.0, 120.0, 119.6, 113.8, HRMS (ESI+) calculated for [M+H] + : [C 22 H 18 N 1 O 3 S 1 ] ; found: IR neat, ν (cm -1 ) 2925 (w), 2850 (w), 1692 (s), 1599 (m), 1447 (m), 1373 (m), 1189 (m), 1177 (s), 1131 (m), 1110 (m), 1088 (w), 1011 (m), 773 (m), 672 (m). S20

21 42 3-(2-(2,2-dibromovinyl)phenyl)-1-tosyl-1H-indole Following the general procedure 4 the product 42 was isolated by FC on silica (EtOAc/pentane 1:8) in 70% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.07 (d, J = 8.3 Hz, 1H), 7.88 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 6.9 Hz, 1H), 7.57 (s, 1H), (m, 5H), (m, 3H), 7.20 (s, 1H), 2.36 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.1, 137.0, 135.1, 134.9, 134.7, 131.6, 130.2, 130.0, 129.9, 129.5, 128.7, 127.5, 127.0, 125.3, 125.0, 123.6, 121.4, 120.4, 113.8, 91.4, 21.6 HRMS (ESI+) calculated for [M+H] + : [C 23 H 18 Br 2 N 1 O 2 S 1 ] ; found: IR neat, ν (cm -1 ) 3373 (m), 1215 (s), 1187 (s), 1181 (s), 764 (m), 749 (m), 611 (m) (4-methoxyphenyl)-7-tosyl-7H-benzo[c]carbazole Following the general procedure 4 the product 43 was isolated by FC on silica (CH 2 Cl 2 /pentane 1:5 to 2:1) in 50% yield as a yellow foam. 1 H NMR (400 MHz, CDCl 3 ) δ 8.54 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 7.6 Hz, 1H), 8.23 (d, J = 7.2 Hz, 1H), 7.98 (d, J = 7.8 Hz, 1H), 7.87 (s, 1H), (m, 2H), (m, 1H), (m, 1H), 7.42 (dtd, J = 16.2, 7.4, 1.1 Hz, 2H), (m, 2H), 6.91 (d, J = 8.3 Hz, 2H), 6.72 (d, J = 8.2 Hz, 2H), 3.88 (s, 3H), 2.09 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.8, 143.9, 141.4, 137.6, 134.7, 133.4, 132.4, 132.2, 130.1, 130.1, 129.0, 128.5, 127.4, 126.8, 126.7, 126.1, 126.0, 125.8, 125.6, 123.4, 122.0, 119.4, 113.9, 55.2, HRMS (ESI+) calculated for [M+H] + : [C 30 H 24 N 1 O 3 S 1 ] ; found: IR neat, ν (cm - 1 ) 3052 (m), 2956 (m), 2932 (m), 2835 (m), 2253 (m), 1609 (m), 1516 (m), 1505 (s), 1373 (s), 1358 (m), 1289 (m), 1245 (m), 1176 (s), 1150 (m), 1089 (m), 1035 (m), 911 (m), 827 (m), 812 (m), 792 (m). S21

22 6. Crystal structure X-Ray structure of 40. CCDC number These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via S22

23 Figure 1: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 11 S23

24 Figure 2: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 12 S24

25 Figure 3: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 13 S25

26 Figure 4: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 14 S26

27 Figure 5: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 15 S27

28 Figure 6: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 16 S28

29 Figure 7: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 17 S29

30 Figure 8: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 18 S30

31 Figure 9: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 19 S31

32 Figure 10: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 20 S32

33 Figure 11: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 21a S33

34 Figure 12: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 21 S34

35 Figure 13: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 23 S35

36 Figure 14: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 24 S36

37 Figure 15: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 25 S37

38 Figure 16: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 26 S38

39 Figure 17: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 27 S39

40 Figure 18: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 28 S40

41 Figure 19: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 29 S41

42 Figure 20: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 30 S42

43 Figure 21: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 31 S43

44 Figure 22: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 32 S44

45 Figure 23: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 33 S45

46 Figure 24: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 34 S46

47 Figure 25: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 35 S47

48 Figure 26: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 36 S48

49 Figure 27: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 37 S49

50 Figure 28: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 38 S50

51 Figure 29: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 39 S51

52 Figure 30: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 40 S52

53 Figure 31: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 41 S53

54 Figure 32: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 42a S54

55 Figure 33: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 42 S55

56 Figure 34: 1 H-NMR (400 MHz) and 13 C-NMR (100 MHz) of 43 S56