Supporting Information for. Selective Double-Carbomagnesiation of Internal Alkynes Catalyzed by Iron-N-Heterocyclic Carbene

Transcription

1 Supporting Information for Selective Double-Carbomagnesiation of Internal Alkynes Catalyzed by Iron-N-Heterocyclic Carbene Complexes: A Convenient Method to Highly Substituted 1,3-Dienyl Magnesium Reagents Yuesheng Liu, Lijun Wang, and Liang Deng* State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, People s Republic of China, deng@sioc.ac.cn S1

2 Table of Contents 1. Experimental Section page S3 2. References page S20 3. Crystal Data and Summary of Data Collection and Refinement for 5 and 15 page S21 4. Molecular structure of 5 page S22 5. GPC Chromatogram page S H and 13 C NMR Spectra page S24 7. Representative NOESY Spectra page S58 8. Representative GC Graphs page S61 S2

3 1. Experimental Setion General Procedures. All experiments were performed under an atmosphere of dry dinitrogen with the rigid exclusion of air and moisture using standard Schlenk or cannula techniques, or in a glovebox. FeCl 2, Fe(acac) 3, MeMgBr, EtMgBr, TMSCH 2 MgBr, D 2 O, PhC CMe, PhC CEt, and MgBr 2 Et 2 O were purchased from Alfa Aesar or Acros Organics and used as received. (IEt 2 Me 2 ) 2 FeMe 2, 1 (IEt 2 Me 2 ) 2 FeCl 2, 1 (IPr 2 Me 2 ) 2 FeCl 2, 1 (IMes) 2 FeCl 2, 2 Bu t CH 2 MgBr, 3 4-CH 3 C 6 H 4 C CMe, 4 4-ClC 6 H 4 C CMe, 4 4-Bu t C 6 H 4 C CMe, 4 4-BrC 6 H 4 C CMe, 4 PhC CBu n, 5 PhC CCy, 5 PhC CBu t, 5 PhC CCH 2 CH=CH 2, 6 and PhC CCH 2 CH 2 CH 2 Cl 7 were prepared according to literature methods. 1 H, 2 D and 13 C NMR spectra were recorded on a VARIAN Mercury 300 MHz, 400 MHz, Agilent 400 MHz or 600 MHz spectrometer. All chemical shifts were reported in units with references to the residual protons of the deuterated solvents for proton chemical shifts, and the 13 C of deuterated solvents for carbon chemical shifts. HRMS-EI spectra were recorded with a Waters Micromass GCT Premier instrument. GC analysis was performed on a Shimadzu GC-2014 spectrometer. GC/MS analysis was performed on a Shimadzu GCMS-QP 2010 Plus spectrometer. Gel Permeation Chromatography (GPC) was carried out in 1,2,4-trichlorobenzene at 135 o C, at a flow rate of 1.0 ml/min, using a PL-GPC220. The molecular weights of polymers were calculated on the basis of a polystyrene calibration. X-Ray Structure Determinations. The structure of the compounds 5 and 15 were determined. Crystallizations were performed at room temperature. Crystals were coated with Paratone-N oil and mounted on a Bruker APEX CCD-based diffractometer. Cell parameters were retrieved with SMART software and refined using SAINT software on all reflections. Data integration was performed with SAINT, which corrects for Lorentz polarization and decay. Absorption corrections were applied using SADABS. 8 Space groups were assigned unambiguously by analysis of symmetry and systematic absences determined by XPREP. The structure was solved and refined using SHELXTL. 9 Metal and first coordination sphere atoms were located from direct-methods E-maps; other non-hydrogen atoms were found in alternating difference Fourier synthesis and least-squares refinement cycles and during final cycles were refined anisotropically. Hydrogen atoms were placed in calculated positions employing a riding model. Final crystal parameters and agreement factors are reported in Table S1. Preparation of Alkynes 1-(2-Methylphenyl)-1-propyne. In a glove box, a glass vessel was charged with 2-methylphenylacetylene (4.04 g, 34.4 mmol), THF (60 ml), and a stir bar. The reaction mixture was cooled to -78 C and a solution of n BuLi (2.5 M in n-hexane, 15 ml, 38 mmol) was added dropwise over a 10 min period. After stirring at the temperature for 1 h, methyl iodide (2.37 ml, 37.8 mmol) was added. The reaction was allowed to proceed for 30 minutes at -78 o C, and then slowly warmed to room temperature. After stirring for another 2 h, the reaction was quenched with water (20 ml). The aqueous phase was extracted with diethylether (3 x 30 ml). The combined organic layers were dried with MgSO 4, filtered, and concentrated under reduced pressure. The purification through distillation under reduced pressure afforded 1-(2-methylphenyl)-1-propyne as a colorless oil (3.81 g, 85% yield). The NMR spectra were identical to S3

4 those reported in literature H NMR (300 MHz, CDCl 3, 302 K): δ (ppm) (m, 1H), (m, 3H), 2.46 (s, 3H), 2.13 (s, 3H). 13 C NMR (75 MHz, CDCl 3, 302 K): δ (ppm) , , , , , , 89.56, 78.54, 20.64, Thienyl-1-propyne. In a glove box, a glass vessel was charged with thienylacetylene (2.21 g, 20.4 mmol), THF (15 ml) and a stir bar. The reaction mixture was cooled to -78 C and a solution of KN(TMS) 2 (1.0 M, 26 ml, 26 mmol) was added dropwise over a 10 min period. After allowing the reaction to stir at the temperature for 1 h, methyl iodide (1.68 ml, 27.0 mmol) was added. The reaction was slowly allowed to warm to room temperature. After stirring for 4 h, the reaction was quenched with water (20 ml). The aqueous phase was extracted with diethylether (3 x 30 ml). The combined organic phase was dried with MgSO 4, filtered, and concentrated under reduced pressure. The purification through distillation under reduced pressure afforded 1-thienyl-1-propyne as a colorless oil (1.56 g, 62% yield). The NMR spectra were identical to those reported in literature H NMR (300 MHz, CDCl 3, 302 K): δ (ppm) (m, 1H), (m, 1H), 7.06 (d, J = 4.9 Hz, 1H), 2.03 (s, 3H). 13 C NMR (75 MHz, CDCl 3, 302 K): δ (ppm) , , , , 85.27, 74.76, (4-Phenyl-3-yn-1-yl)-1,3-dioxane. In a glove box, a glass vessel was charged with copper(ii) chloride (0.040 g, 0.30 mmol), 1-chloro-2-phenylacetylene (1.37 g, 10.0 mmol), THF (8 ml) and a stir bar. The reaction mixture was cooled to 0 C and a solution of (1,3-dioxan-2-ylethyl)magnesium bromide freshly prepared from the interaction of 2-(2-bromoethyl)-1,3-dioxane (2.34 g, 12.0 mmol) with magnesium (0.50 g, 21 mmol) was added slowly over a 15 min period. After the addition, the mixture was further stirred at 0 C for 1 h. The reaction mixture was then quenched with water (20 ml). The aqueous phase was extracted with CH 2 Cl 2 (3 x 20 ml). The combined organic phase was dried with MgSO 4, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (hexane/ea =10:1) to yield 2-(4-phenyl-3-yn-1-yl)-1,3-dioxane as a light yellow oil. Further purification through distillation under reduced pressure afforded pure 2-(4-phenyl-3-yn-1-yl)-1,3-dioxane as a colorless oil (0.50 g, 23% yield). 1 H NMR (400 MHz, CDCl 3, 293 K): δ (ppm) (m, 2H), (m, 3H), 4.69 (t, J = 5.2 Hz, 1H), 4.11 (dd, J = 11.2, 4.6 Hz, 2H), (m, 2H), 2.5 (t, J = 7.2 Hz, 2H), (m, 1H), 1.87 (td, J = 7.3, 5.6 Hz, 2H), (m, 1H). 13 C NMR (100 MHz, CDCl 3, 293 K): δ (ppm) , , , , , 89.30, 80.61, 66.89, 34.07, 25.79, HRMS (EI): calcd for [C 14 H 16 O 2 ] + : ; Found: S4

5 Typical Procedures for Catalyst Screening. A glass vessel was charged with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), n-dodecane (0.085 g, 0.50 mmol), 0.05 mmol of the catalyst, THF (0.50 ml), and a stir bar. To the solution, a solution of MeMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol) was added in one portion. The mixture was stirred for 15 min, and then quenched by water (1 ml). The resulting mixture was extracted with diethylether (5 ml). The organic phase was then dried over MgSO 4, analysed by gas chromatography-mass spectrometer (GC-MS) to confirm the identity of the products, and further analysed by GC with a flame ionization detector (GC-FID) to quantify the yields with n-dodecane as the internal standard. The conversion of the alkyne, and the yields of 1a and 2 referred to the alkyne were summarized in Table 1. FeCl 2 /IPr-Catalyzed Reaction of 1-Phenyl-1-propyne with MeMgBr. A glass vessel was charged with IPr (0.039 g, 0.10 mmol), FeCl 2 (0.006 g, mmol), THF (0.50 ml) and a stir bar. The mixture was stirred for 10 min at room temperature. To the solution was added 1-phenyl-1-propyne (0.116 g, 1.00 mmol), and then MeMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol). After stirring for 15 min, the mixture became dark brown and thick. The mixture was quenched with water (1 ml), extracted with toluene (5 ml 3), and then filtered. The addition of the filtrate to methanol (25 ml) led to the formation of a white flocculent precipitate. Further filtration and dried in vacuum afforded poly(1-phenyl-1-propyne) as a light yellow solid (0.047 g, Yield: 41%). The 1 H NMR spectrum (Figure S3) of the polymer is identical to that reported in literature. 12 The GPC spectrum is shown in Figure S2. Gel Permeation Chromatography (GPC) data: M P : , M n : 77791, M v : , M w : , M z, , M z+1 : , PD, H NMR (300 MHz, CDCl 3, 302 K): δ (ppm) (5H), (3H). IR (KBr, cm -1 ): ν = 3080 (w), 3053 (w), 2958 (w), 2930 (w), 2906 (w), 2870 (w), 2849 (w), 1944 (w), 1878 (w), 1837 (w), 1597 (w), 1574 (w), 1491 (w), 1439 (w), 1371 (w), 1260 (m), 1179 (w), 1156 (w), 1074 (w), 1029 (w), 909 (w), 845 (s), 802 (w), 765 (m), 696 (s), 616 (w). (IEt 2 Me 2 ) 2 FeCl 2 -Catalyzed Double Carbometallation of 1-Phenyl-1-propyne with MeMgBr and the Transformations of the Resultant 1,3-Dienyl Grignard Reagent. A glass vessel was charged with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), 0.50 ml THF, and a stir bar. To the solution was added MgMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol). The color of the solution changed to red brown quickly. After 15 min, the mixture was quenched with H 2 O (1 ml), and extracted with CH 2 Cl 2 (5 ml 3). The combined organic phase was dried over anhydrous MgSO 4, filtered, and concentrated under reduced pressure to leave a brown residue. Column chromatographic separation on silica gel with n-hexane as eluent afforded 1a as a colorless oil (0.094 g, 76% yield). S5

6 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 4H), 6.44 (s, 1H), 1.93 (s, 3H), 1.79 (d, J = 1.6 Hz, 3H), 1.70 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 22.21, 21.83, HRMS (EI): calcd for [C 19 H 20 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3055 (w), 3021 (w), 2983 (w), 2908 (w), 2854 (w), 2724 (w), 1946 (w), 1881 (w), 1806 (w), 1598 (w), 1490 (w), 1441 (m), 1372 (w), 1261 (w), 1069 (m), 1029 (w), 916 (w), 803 (w), 767 (m), 748 (m), 697 (s). The deuterated water-quenching experiment was conducted with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), MgMgBr (1.4 M in THF/Toluene, 0.50 ml, 0.70 mmol), and D 2 O (0.5 ml) using procedures identical to that used for the preparation of 1a.Yiled of 1a-D: g, 82% yield. 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 4H), (m, 2H), (m, 4H), 1.85 (s, 3H), 1.71 (s, 3H), 1.62 (s, 3H). 2 H NMR (92 MHz, CDCl 3, 298 K): δ (ppm) C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , (t, J = 23.4 Hz), , , , , , 22.23, 21.84, HRMS (EI): calcd for [C 19 H 2 19 H] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3056 (w), 3022 (w), 2982 (w), 2909 (w), 2854 (w), 2724 (w), 1947 (w), 1883 (w), 1807 (w), 1759 (w), 1705 (w), 1598 (w), 1490 (w), 1442 (m), 1373 (w), 1262 (w), 1069 (m), 1029 (w), 917 (w), 803 (w), 748 (m), 697 (s). The iodine-quenching experiment was conducted with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), MgMgBr (1.4 M in THF/Toluene, 0.50 ml, 0.70 mmol), and I 2 (0.75 mol). After the preparation of the 1,3-dienyl magnesium reagent, the mixture was cooled to -5 C in the ice bath and a THF solution of I 2 (0.75 mmol) was added. The reaction was stirred for 2 h at the temperature, and then extracted with CH 2 Cl 2 (5 ml 3). The combined organic portions were dried over anhydrous MgSO 4, filtered, and concentrated under vacuum to remove the solvent. The residue was subjected to silica gel column chromatography (n-hexane as eluent) to afford 3a as a white solid (0.122 g, 65% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 2H), (m, 8H), 1.95 (s, 3H), 1.76 (s, 3H), 1.66 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , 97.45, 21.83, 21.31, HRMS (EI): calcd for [C 19 H 19 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3056 (w), 3021 (w), 2978 (w), 2907 (w), 2850 (w), 2719 (w), 2124 (w), 1947 (w), 1886 (w), 1719 (w), 1597 (w), 1488 (w), 1440 (m), 1369 (w), 1261 (w), S6

7 1068 (w), 1026 (w), 1007 (w), 845 (w), 804 (w), 753 (s), 695 (s), 652 (w). The parafomaldehdye-quenching experiment was conducted with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), MgMgBr (1.4 M in THF/Toluene, 0.50 ml, 0.70 mmol) and and (CH 2 O) n (0.022 g, 0.70 mmol). After the preparation of the 1,3-dienyl magnesium reagent, (CH 2 O) n was added. The mixture was then stirred at 50 o C for 2 h, quenched with water (1 ml), and then extracted with CH 2 Cl 2 (5 ml 3). The combined organic portions were dried over anhydrous MgSO 4, filtered, and concentrated under vacuum to remove the solvent. The residue was subjected to silica gel column chromatography (EtOAc : hexane = 2 : 1 as eluent) to afford 4 as a white solid (0.093 g, 67% yield). 1 H NMR (400 MHz, CDCl 3, 295 K): δ (ppm) (m, 4H), (m, 6H), 4.58 (d, J = 12.0 Hz, 1H), 4.43 (d, J = 11.9 Hz, 1H), 1.89 (s, 3H), 1.80 (s, 3H), 1.57 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 64.51, 21.81, 21.25, HRMS (EI): calcd for [C 20 H 22 O] + : ; Found: IR (KBr, cm -1 ): ν = 3581 (w, O-H), 3452 (w), 3077 (w), 3055 (w), 3021 (w), 2980 (w), 2909 (w), 2855 (w), 2723 (w), 1949 (w), 1885 (m), 1810 (w), 1719 (m), 1598 (w), 1490 (m), 1441 (w), 1372 (w), 1261 (w), 1183 (w), 1094 (w), 1067 (w), 1020 (w), 1002 (w), 914 (w), 803 (w), 769 (w), 738 (w), 738 (w), 701(s). A glass vessel was charged with 4 (0.400 g, 1.44 mmol), NEt 3 (0.22 ml, 1.6 mmol), CH 2 Cl 2 (15 ml) and a stir bar. The solution was cooled in an ice bath, and was added 4-nitrobenzoyl chloride (0.270 g, 1.46 mmol). The mixture was allowed to warm to room temperature and further stirred for 6 h, then quenched with water (10 ml). After extraction with CH 2 Cl 2 (5 ml 3), the combined organic portions were dried over anhydrous MgSO 4, filtered, and concentrated under vacuum to leave a brown solid. The residue was purified by silica gel column chromatography (CH 2 Cl 2 : n-hexane = 3 : 1 as eluent) to afford 5 as a white solid (0.487 g, 79% yield). 1 H NMR (400 MHz, CDCl 3, 295 K): δ (ppm) 8.23 (d, J = 8.5 Hz, 2H), 8.01 (d, J = 8.5 Hz, 2H), (m, 10H), (m, 2H), 1.91 (s, 3H), 1.79 (s, 3H), 1.63 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 295 K): δ (ppm) (C=O), , , , , , , , , , , , , , , , , 67.69, 21.93, 21.42, HRMS (EI): calcd for [C 27 H 25 NO 4 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3057 (w), 3015 (w), 2982 (w), 2941 (w), 2913 (w), 2852 (w), 2713 (w), 1947 (w), 1708 (m), 1599 (w), 1523 (m), 1488 (w), 1439 (m), 1344 (w), 1270 (s), 1120 (w), 1110 (w), 938 (w), 869 (w), 840 (w), 770 (s), 738 (w), 719 (s), 699 (s), 667 (w). S7

8 The cross-coupling experiment was conducted with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), MgMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol), and CH 2 =CHCH 2 Br (0.085 g, 0.70 mmol). After the preparation of the 1,3-dienyl magnesium reagent, CH 2 =CHCH 2 Br was added. The mixture was then stirred at 50 o C for 30 min, quenched with water (1 ml), and then extracted with CH 2 Cl 2 (5 ml 3). The combined organic portions were dried over anhydrous MgSO 4, filtered, and concentrated under vacuum to remove the solvent. The residue was subjected to silica gel column chromatography (n-hexane as eluent) to afford the cross-coupling product 6 as a colorless oil (0.096 g, 67% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 2H), (m, 2H), 5.53 (ddt, J = 17.1, 10.3, 6.9 Hz, 1H), (m, 2H), (m, 2H), 1.78 (s, 3H), 1.69 (s, 3H), 1.43 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , , , 40.02, 22.00, 21.35, HRMS (EI): calcd for [C 22 H 24 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3056 (w), 3023 (w), 2977 (w), 2925 (w), 2909 (w), 2854 (w), 2723 (w), 1948 (w), 1883 (w), 1808 (w), 1721 (w), 1678 (w), 1598 (w), 1490 (w), 1441 (w), 1372 (w), 1261 (w), 1178 (w), 1156 (w), 1070 (w), 1028 (w), 912 (w), 749 (w), 698 (s). General Procedure for the Preparation of Highly Substituted 1,3-Dienes from Iron-Catalyzed Double-Carbometalation of Alkynes. In a glove box, a glass vessel was charged with alkyne (1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), THF or toluene (0.50 ml), and a stir bar. To the solution was added Grignard reagent R MgBr (0.70 mmol). With vigorous stirring, the color of the solution changed to red brown quickly. The resulting reaction mixture was stirred for the indicated time at room temperature or 0 o C, then quenched with water (1 ml). After extraction with CH 2 Cl 2 (5 ml 3), the combined organic portions were dried over anhydrous MgSO 4, and filtered. The solvent were removed, and the residue was purified by silica gel column chromatography to yield the dienes. General Procedure for Synthesis of Highly Substituted 1,3-Dienyl Iodides from Iron-Catalyzed Carbometalation of Alkynes. In a glove box, a glass vessel was charged with alkyne (1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), THF or toluene (0.50 ml), and a stir bar. To the solution was added MeMgBr (1.4 M in THF/Toluene, 0.50 ml, 0.70 mmol). With vigorous stirring, the color of the solution changed to red brown quickly. The resulting reaction mixture was stirred for the indicated time at room temperature or 0 o C. After cooled to -5 C in an ice bath, a THF solution of I 2 (0.75 mmol) was added. The S8

9 mixture was stirred for 2 h at the temperature, then was quenched with water (1 ml). After extraction with CH 2 Cl 2 (5 ml 3), the combined organic portions were dried over anhydrous MgSO 4 and filtered. The solvent were removed, and the residue was purified by silica gel column chromatography to yield the dienyl iodide. 1b. The reaction was carried out according to the typical procedure by using: 1-(4-methylphenyl)-1-propyne (0.130 g, 1.00 mmol) and MeMgBr (1.4 M, 0.72 ml, 1.0 mmol) for 60 min in THF at ice bath. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.113 g, 82% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) 7.15 (d, J = 8.0 Hz, 2H), (m, 6 H), 6.30 (s, 1H), 2.25 (s, 6H), 1.83 (s, 3H), 1.69 (d, J = 1.2 Hz, 3H), 1.63(s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 22.24, 21.85, 21.15, 21.13, HRMS (EI): calcd for [C 21 H 24 ] + : ; Found: IR (KBr, cm -1 ): ν = 3081 (w), 3045 (w), 3020 (w), 2983 (w), 2919 (w), 2856 (w), 2726 (w), 1904 (w), 1610 (m), 1510 (w), 1444 (w), 1373 (m), 1260 (m), 1180 (w), 1073 (w), 1021 (w), 863 (w), 806 (s), 727 (s). 1c. The reaction was carried out according to the typical procedure by using: 1-(4-tert-butylphenyl)-1-propyne (0.172 g, 1.00 mmol) and MeMgBr (1.4 M, 0.72 ml, 1.0 mmol) for 60 min in THF at ice bath. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.153 g, 85% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) 7.37 (dt, J = 8.8, 2.0 Hz, 2H), (m, 4H), 7.15 (dt, J = 8.4, 1.8 Hz, 2H), 6.38 (s, 1H), 1.90 (s, 3H), 1.81 (d, J = 1.2 Hz, 3H), 1.72 (s, 3H), 1.33 (s, 9H), 1.31 (s, 9H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 34.48, 34.41, 31.41, 31.34, 22.27, 21.92, HRMS (EI): calcd for [C 27 H 36 ] + : ; Found: IR (KBr, cm -1 ): ν = 3082 (w), 3049 (w), 3029 (w), 2960 (w), 2906 (s), 2866 (w), 2722 (w), 1909 (w), 1702 (m), 1506 (w), 1461 (w), 1363 (m), 1269 (m), 1201 (w), 1110 (m), 1072 (w), 1019 (w), 865 (m), 831 (s), 706 (s). S9

10 3c. The reaction was carried out according to the typical procedure by using: 1-(4-tert-butylphenyl)-1-propyne (0.172 g, 1.00 mmol), MeMgBr (1.4 M, 0.72 ml, 1.0 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.180 g, 74% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 4H), (m, 2H), (m, 2H), 1.98 (s, 3H), 1.83 (s, 3H), 1.72 (s, 3H), 1.38 (s, 9H), 1.36 (s, 9H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 97.91, 34.57, 34.49, 31.40, 31.31, 21.88, 21.42, HRMS (EI): calcd for [C 27 H 35 I] + : ; Found: IR (KBr, cm -1 ): ν = 3081 (w), 3027 (w), 2963 (s), 2905 (w), 2866 (w), 2721 (w), 1907 (w), 1601 (w), 1503 (w), 1462 (w), 1442 (w), 1394 (w), 1363 (w), 1268 (w), 1223 (w), 1201 (w), 1109 (w), 1072(w), 1021 (w), 1010 (w), 934 (w), 862 (w), 834 (w), 821 (w), 758 (w), 739 (w), 713 (w), 649 (w), 600 (w), 564 (w). 1d. The reaction was carried out according to the typical procedure by using: 1-(4-bromophenyl)-1-propyne (0.195 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in toluene at ice bath. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.142 g, 70% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 4H), (m, 2H), (m, 2H), 6.33 (s, 1H), 1.90 (s, 3H), 1.74 (d, J = 1.6 Hz, 3H), 1.68 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 22.23, 21.82, HRMS (EI): calcd for [C 19 H 18 Br 2 ] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3023 (w), 2980 (w), 2909 (w), 2853 (w), 2724 (w), 1902 (w), 1781 (m), 1710 (w), 1633 (w), 1585 (w), 1483 (s), 1442 (m), 1393 (m), 1178 (w), 1101 (w), 1071 (s), 1008 (s), 894 (w), 861 (m), 821 (s), 799 (s), 735 (w). 1e. The reaction was carried out according to the typical procedure by using: 1-(4-cholorophenyl)-1-propyne (0.151 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) for 60 min S10

11 in toluene at ice bath. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.112 g, 70% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 2H), 6.27 (s, 1H), 1.81 (s, 3H), 1.65 (d, J = 1.6 Hz, 3H), 1.60 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 22.22, 21.80, HRMS (EI): calcd for [C 19 H 18 Cl 2 ] + : ; Found: IR (KBr, cm -1 ): ν = 3079 (w), 3027 (w), 2983 (w), 2910 (w), 2855 (w), 2725 (w), 1902 (w), 1707 (w), 1632 (w), 1592 (w), 1487 (s), 1444 (m), 1398 (m), 1374 (w), 1091 (s), 1014 (m), 862 (w), 827 (m), 804 (m), 743 (w), 722 (w). 3e. The carbometalation reaction was carried out according to the typical procedure by using: 1-(4-cholorophenyl)-1-propyne (0.151 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.148 g, 67% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 6H), (m, 2H), 1.94 (s, 3H), 1.76 (s, 3H), 1.67 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 96.16, 21.80, 21.26, HRMS (EI): calcd for [C 19 H 17 Cl 2 I] + : ; Found: IR (KBr, cm -1 ): ν = 2982 (w), 2937 (w), 2907 (w), 2851 (w), 1588 (w), 1486 (w), 1440 (w), 1395 (w), 1369 (w), 1091 (w), 1072 (w), 1014 (w), 858 (w), 817 (w), 747 (w), 722 (w). 8. The reaction was carried out according to the typical procedure by using: 1-thienyl-1-propyne (0.112 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at Room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.070 g, 54% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) 7.20 (dd, J = 4.9, 3.0 Hz, 1H), 7.15 (dd, J = 4.8, 3.1 Hz, 1H), 7.09 (d, J = 2.6 Hz, 1H), 7.06 (dd, J = 5.0, 0.9 Hz, 1H), 6.96 (dd, J = 2.9, 1.0 Hz, 1H), 6.90 (dd, J = 4.9, 1.1 Hz, 1H), 6.27 (s, 1H), 1.80 (s, 3H), 1.79 (d, J = 1.2 Hz, 3H), 1.73 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 22.38, 22.02, HRMS (EI): calcd for [C 15 H 16 S 2 ] + : ; Found: IR (KBr, cm -1 ): ν = 3103 (w), 2981 (w), 2907 (w), 2853 (w), 2721 (w), 1761 (w), 1634 (w), 1567 (w), 1520 (w), 1442 (s), 1407 (w), 1370 (w), 1330 (w), 1260 (w), 1219 (w), 1162 (w), 1071 (w), 1024 (w), 934 (w), 841 (m), 780 (s), 681 (m), 627 (m). S11

12 9. The reaction was carried out according to the typical procedure by using: 1-thienyl-1-propyne (0.112 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.079 g, 41% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), 7.24 (dd, J = 2.9, 1.1 Hz, 1H), 7.21 (dd, J = 3.0, 1.2 Hz, 1H), 7.18 (dd, J = 4.9, 1.2 Hz, 1H), 7.13 (dd, J = 5.0, 1.2 Hz, 1H), 1.88 (s, 3H), 1.86 (s, 3H), 1.82 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 90.97, 21.64, 21.41, HRMS (EI): calcd for [C 15 H 15 IS 2 ] + : ; Found: IR (KBr, cm -1 ): ν = 3102 (w), 2979 (w), 2907 (w), 2852 (w), 1441 (w), 1404 (w), 1368 (w), 1220 (w), 1167 (w), 1080 (w), 1019 (w), 939 (w), 868 (w), 846 (w), 837 (w), 781 (s), 745 (w), 684 (w), 661 (w), 634 (w). 10. The reaction was carried out according to the typical procedure by using: 1-phenyl-1-butyne (0.130 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.112 g, 81% yield). 1 H NMR (400 MHz, CDCl 3, 295 K): δ (ppm) (m, 6H), (m, 4 H), 6.46 (s, 1H), (m, 4H), 1.96 (s, 3H), (m, 6H). 13 C NMR (100 MHz, CDCl 3, 295 K): δ (ppm) , , , , , , , , , , , , 28.06, 23.13, 19.13, 13.39, HRMS (EI): calcd for [C 21 H 24 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3056 (w), 3022 (w), 2968 (m), 2933 (w), 2873 (w), 2725 (w), 1946 (w), 1887 (w), 1806 (w), 1761 (w), 1598 (w), 1575 (w), 1492 (w), 1445 (m), 1375 (w), 1276 (w), 1071 (m), 1029 (w), 1001 (w), 921 (w), 875 (w), 840 (w), 761 (m), 749 (m), 701 (s), 656 (w), 621 (w). 11. The reaction was carried out according to the typical procedure by using: 1-phenyl-1-butyne (0.130 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.141 g, 70% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), (m, 7H), (m, 1H), (m, 3H), 1.99 (s, 3H), (m, 1H), 1.06 (t, J = 7.5 Hz, 3H), 0.87 (t, J = 7.5 Hz, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 97.88, 27.75, 25.97, 19.23, 12.68, HRMS (EI): calcd for [C 21 H 23 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3055 (w), 3017 (w), 2967 (s), 2931 (w), 2872 (w), 1944 (w), 1880 (w), 1597 (w), 1441 (w), 1373 (w), 1262 (w), 1209 (w), 1184 (w), 1155 (w), 1099 (w), 1071 (w), 1050 S12

13 (w), 1028 (w), 823 (w), 805 (w), 699 (s), 659 (w), 559 (w). 12. The reaction was carried out according to the typical procedure by using: 1-phenyl-1-hexyne (0.158 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.112 g, 66% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 4 H), 6.36 (s, 1H), (m, 4H), 1.84 (s, 3H), (m, 4H), (m, 4H), 0.74 (q, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , 34.69, 30.76, 30.20, 29.87, 22.92, 22.51, 19.63, 14.01, HRMS (EI): calcd for [C 25 H 32 ] + : ; Found: IR (KBr, cm -1 ): ν = 3078 (w), 3056 (w), 3022 (w), 2957 (m), 2859 (m), 1598 (w), 1491 (w), 1465 (w), 1443 (w), 1377 (w), 1072 (m), 917 (w), 765 (m), 751(m), 700 (s). 13. The reaction was carried out according to the typical procedure by using: 1-phenyl-1-hexyne (0.158 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.140 g, 61% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), (m, 7H), (m, 1H), (m, 3H), 2.00 (s, 3H), (m, 1H), (m, 3H), (m, 3H), (m, 2H), 0.84 (t, J = 7.3 Hz, 3H), 0.73 (t, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 97.87, 34.40, 32.60, 30.20, 30.14, 22.85, 22.55, 19.81, 13.94, HRMS (EI): calcd for [C 25 H 31 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3055 (w), 3017 (w), 2957 (s), 2926 (w), 2858 (w), 1944 (w), 1873 (w), 1597 (w), 1489 (w), 1465 (w), 1441 (w), 1377 (w), 1260 (w), 1204 (w), 1176 (w), 1097 (w), 1072 (w), 1028 (w), 850 (w), 803 (w), 757 (w), 700 (w), 660 (w), 559 (w). 14. The reaction was carried out according to the typical procedure by using: 1-cyclohexyl-2-phenylethyne (0.184 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.108 g, 56% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 10H), 6.30 (s, 1H), 2.69 (tt, J = 11.8, 2.8 Hz, 1H), 2.44 (tt, J = 11.6, 3.2 Hz, 1H), 1.80 (s, 3H), (m, 12H), (m, 6H), (m, 2H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , S13

14 128.24, , , , , 41.60, 41.04, 26.54, 26.31, 26.22, 26.03, HRMS (EI): calcd for [C 29 H 36 ] + : ; Found: IR (cm -1 ): ν = 3056 (w), 3021 (w), 2978 (m), 2928 (w), 2852 (w), 1723 (w), 1598 (w), 1447 (m), 1153 (w), 1123 (w), 1073 (m), 1031 (w), 1013 (w), 919 (w), 891 (w), 841 (w), 752(m), 701(m). 15. The reaction was carried out according to the typical procedure by using: 1-cyclohexyl-2-phenylethyne (0.184 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a white solid (0.151 g, 59% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), (m, 8H), 2.68 (tt, J = 12.6, 3.0 Hz, 1H), 2.32 (tt, J = 12.1, 3.1 Hz, 1H), 1.94 (s, 3H), (m, 2H), (m, 6H), (m, 5H), (m, 2H), (m, 2H), 0.79 (qt, J = 12.8, 3.2 Hz, 1H), 0.66 (qt, J = 12.8, 3.2 Hz, 1H), 0.35 (qd, J = 12.8, 3.4 Hz, 1H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 99.93, 43.91, 41.90, 33.35, 32.29, 30.62, 29.77, 26.82, 26.37, 26.34, 26.29, 26.18, 25.70, HRMS (EI): calcd for [C 29 H 35 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3046 (w), 3024 (w), 2928 (s), 2851 (s), 1597 (w), 1573 (w), 1489 (w), 1443 (w), 1374 (w), 1349 (w), 1307 (w), 1261 (w), 1201 (w), 1169 (w), 1070 (w), 1027 (w), 889 (w), 861 (w), 784 (w), 756 (w), 723 (w), 701 (w), 649 (w), 555 (w). 16. The reaction was carried out according to the typical procedure by using: 1-phenyl-3,3-dimethyl-1-butyne (0.158 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.015 g, 9% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 5H), (m, 5H), 5.49 (s, 1H), 2.01 (s, 3H), 1.25 (s, 9H), 1.02 (s, 9H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 37.22, 34.87, 31.18, 30.04, HRMS (EI): calcd for [C 25 H 32 ] + : ; Found: IR (KBr, cm -1 ): ν = 3078 (w), 3056 (w), 2956 (s), 2867 (w), 1744 (w), 1597 (w), 1487 (m), 1468 (w), 1444 (w), 1236 (w), 1194 (w), 1075 (w), 983 (w), 898 (w), 781 (w), 754 (w), 701(s). 17. The reaction was carried out according to the typical procedure by using: 1-phenyl-pent-4-en-1-yne (0.142 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification S14

15 by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.089 g, 60% yield). 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 10H), 6.64 (s, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), 2.93 (dq, J = 6.6, 0.8 Hz, 2H), 2.85 (dt, J = 6.2, 1.4 Hz, 2H), 2.01 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , , , , , 39.71, 34.97, HRMS (EI): calcd for [C 23 H 24 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3058 (w), 3023 (w), 2976 (w), 2929 (w), 2858 (w), 1951 (w), 1727 (w), 1635 (w), 1491 (w), 1442 (w), 1379 (w), 1152 (m), 1118 (s), 1073 (w), 1027 (w), 992 (w), 911 (m), 844 (m), 752 (m), 699 (s). 18. The reaction was carried out according to the typical procedure by using: 1-phenyl-pent-4-en-1-yne (0.142 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.125 g, 59% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), (m, 8H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 3H), (m, 1H), 2.01 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , , , , , 99.30, 39.36, 37.49, HRMS (EI): calcd for [C 23 H 23 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3066 (w), 3017 (w), 2976 (w), 2907 (w), 2849 (w), 1948 (w), 1826 (w), 1636 (w), 1597 (w), 1574 (w), 1489 (w), 1411 (w), 1374 (w), 1262 (w), 1230 (w), 1204 (w), 1178 (w), 1156 (w), 1072 (w), 1030 (w), 992 (w), 913 (w), 847 (w), 803 (w), 773 (w), 761 (w), 700 (w), 652 (w), 629 (w), 612 (w), 594 (w), 559 (w). 19. The reaction was carried out according to the typical procedure by using: 2-(4-phenyl-3-yn-1-yl)-1,3-dioxane (0.216 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography afforded the title compound as a colorless oil (0.170 g, 76% yield). 1 H NMR (400 MHz, CDCl 3, 295 K): δ (ppm) (m, 6H), (m, 4H), 6.37 (s, 1H), (m, 2H), (m, 4H), (m, 4H), (m, 4H), (m, 2H) (s, 3H), (m, 4H), (m, 2H). 13 C NMR (100 MHz, CDCl 3, 295 K): δ (ppm) , , , , , , , , , , , , , , 66.73, 66.72, 33.95, 33.25, 29.50, 25.71, 25.68, 24.56, HRMS (EI): calcd for [C 29 H 36 O 4 ] + : ; Found: IR (KBr, cm -1 ): ν = 3054 (w), 3022 (w), 2964 (w), 2928 (w), 2850 (w), 2730 (w), 1598 (w), 1491 (w), 1442 (s), 1378 (w), 1285 (w), 1239 (w), 1142 (m), 1080 (m), 1037 (w), 1001 (m), 925 (w), 888 (m), 851 (w), 751 (m), S15

16 700 (s). The reaction was carried out according to the typical procedure by using: 2-(4-phenyl-3-yn-1-yl)-1,3-dioxane (0.216 g, 1.00 mmol), MeMgBr (1.4 M, 0.50 ml, 0.70 mmol), and I 2 (0.75 mmol). Purification by silica gel chromatography afforded the title compound as a colorless oil (0.170 g, 60% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 2H), (m, 8H), 4.46 (t, J = 5.3 Hz, 1H), 4.21 (t, J = 5.1 Hz, 1H), (m, 4H), (m, 4H), (m, 1H), (m, 1H), (m, 2H), 1.98 (s, 3H), (m, 1H), (m, 4H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , , , 98.79, 66.74, 66.63, 66.61, 66.56, 33.24, 33.10, 29.03, 27.25, 25.71, 25.54, HRMS (EI): calcd for [C 29 H 35 IO 4 ] + : ; Found: IR (KBr, cm -1 ): ν = 2872 (w), (w), (w), (w), (w), (w), (w), (s), (w), (w), (w), (w), (w), (w), (w), (s). 21. The reaction was carried out according to the typical procedure by using: 1-phenyl-5-chloro-1-pentyne (0.179 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol). Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a colorless oil (0.064 g, 34% yield). 1 H NMR (400 MHz, CDCl 3, 295 K): δ (ppm) (m, 6H), (m, 4H), 6.43 (s, 1H), (m, 4H), (m, 4H), 1.88 (s, 3H), ,74 (m, 4H). 13 C NMR (100 MHz, CDCl 3, 295 K): δ (ppm) , , , , , , , , , , , , 44.91, 44.66, 32.56, 31.62, 31.14, 27.69, HRMS (EI): calcd for [C 23 H 26 Cl 2 ] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3056 (w), 3022 (w), 2991 (w), 2956 (w), 2854 (w), 1598 (w), 1491 (w), 1443 (w), 1306 (w), 1276 (w), 1072 (w), 1002 (w), 920 (w), 751 (m), 701 (s), 652 (w). 22. The reaction was carried out according to the typical procedure by using: 1-phenyl-5-chloro-1-pentyne (0.179 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as a white solid (0.065 g, 26% yield). S16

17 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 7H), (m, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 2.01 (s, 3H), (m, 2H), (m, 2H), (m, 1H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , 99.33, 44.90, 44.37, 32.06, 31.06, 30.95, 30.27, HRMS (EI): calcd for [C 23 H 25 Cl 2 I] + : ; Found: IR (KBr, cm -1 ): ν = 3076 (w), 3054 (w), 3018 (w), 2955 (w), 2852 (w), 1949 (w), 1882 (w), 1807 (w), 1597 (w), 1574 (w), 1489 (w), 1441 (w), 1376 (w), 1306 (w), 1274 (w), 1202 (w), 1155 (w), 1070 (w), 1028 (w), 969 (w), 917 (w), 865 (w), 759 (w), 702 (w), 651 (w), 559 (w), 529 (w). 23. The reaction was carried out according to the typical procedure by using: diphenylacetylene (0.178 g, 1.00 mmol) and MeMgBr (1.4 M, 0.50 ml, 0.70 mmol) in THF at room temperature. Purification by silica gel chromatography (n-hexane as eluent) afforded the title compound as awhite solid (0.037 g, 20% yield). 1 H NMR (400 MHz, CDCl 3, 292 K): δ (ppm) (m, 15H), (m, 5H), 6.79 (s, 1H), 2.40 (s, 3H). 13 C NMR (100 MHz, CDCl 3, 292 K): δ (ppm) , , , , , , , , , , , , , , , , , , HRMS (EI): calcd for [C 29 H 24 ] + : ; Found: IR (KBr, cm -1 ): ν = 3074 (w), 3018 (w), 2911 (w), 2852 (w), 1946 (w), 1874 (w), 1806 (w), 1746 (w), 1597 (w), 1574 (w), 1489 (w), 1441 (m), 1371 (w), 1329 (w), 1261 (w), 1170 (w), 1156 (w), 1104 (w), 1073 (w), 1028 (w), 977 (w), 921 (m), 910 (w), 862 (w), 846 (w), 824 (w), 790 (w), 761 (w), 742 (w), 694 (s), 639 (w), 616 (w), 567 (w), 541 (w), 514 (w), 460 (w). 24. In a glovebox, a glass vessel was charged with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), THF (0.5 ml) and a stir bar. To the solution was added TMSCH 2 MgBr (1.0 M in THF, 0.70 ml, 0.70 mmol). There was a obvious color change from colorless to yellow. The reaction was stirred for 8 h at 50 o C, during which time the solution turn to thickness, and there a gradual color change from yellow to brown. Then the resulting mixture was quenched with water. After extraction with CH 2 Cl 2 (5 ml 3), the combined organic portions were dried over anhydrous MgSO 4 and filtered. The solvent were removed, and the residue was purified by silica gel column chromatography (n-hexane as eluent) to afford the title compound as a colorless oil (0.040 g, 25% yield) 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 4H), 6.48 (s, 1H), 1.94 (s, 2H), 1.82 (d, J = 1.4 Hz, 3H), 1.69 (s, 3H), 0.12 (s, 9H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 26.57, 22.27, 18.44, HRMS (EI): calcd for [C 22 H 28 Si] + : ; Found: IR (KBr, cm -1 ): ν = 3077 (w), 3057 (w), 3023 (w), 2953 (w), 2857 (w), 2728 (w), 1946 (w), 1729 (w), 1679 (w), 1599 (w), 1443 (w), 1374 (w), 1247 (m), 1158 (w), 1071 (w), 1025 (w), 838 (s), 749 (m), 697 (s). S17

18 25. In a glovebox, a glass vessel was charged with 1-phenyl-1-propyne (0.116 g, 1.00 mmol), (IEt 2 Me 2 ) 2 FeCl 2 (0.022 g, mmol), THF (0.50 ml) and a stir bar. To the solution was added Bu t CH 2 MgBr (1.0 M in THF, 0.70 ml, 0.70 mmol). There was a obvious color change from colorless to yellow. The reaction was stirred for 8 h at 50 o C, during which time the solution turn to thickness, and there a gradual color change from yellow to brown. Then the resulting mixture was quenched with water. After extraction with CH 2 Cl 2 (5 ml 3), the combined organic portions were dried over anhydrous MgSO 4 and filtered. The solvent were removed, and the residue was purified by silica gel column chromatography (n-hexane as eluent) to afford the title compound as a colorless oil (0.021 g, 14% yield) 1 H NMR (400 MHz, CDCl 3, 294 K): δ (ppm) (m, 6H), (m, 4H), 6.39 (s, 1H), 2.34 (s, 2H), 1.71 (s, 3H), 1.65 (s, 3H), 0.93 (s, 9H). 13 C NMR (100 MHz, CDCl 3, 294 K): δ (ppm) , , , , , , , , , , , , 48.18, 32.22, 30.94, 22.98, HRMS (EI): calcd for [C 23 H 28 ] + : ; Found: IR (KBr, cm -1 ): ν = 3078 (w), 3057 (w), 3022 (w), 2954 (m), 1945 (w), 1729 (w), 1598 (w), 1531 (w), 1490 (w), 1466 (w), 1442 (w), 1391 (w), 1375 (w), 1364 (w), 1233 (m), 1185 (w), 1155 (w), 1138 (w), 1122 (w), 1097 (w), 1073 (w), 1057 (w), 1030 (w), 1016 (w), 917 (w), 873 (w), 843 (w), 803 (w), 769 (w), 751 (w), 700 (s). The Reaction of (IEt 2 Me 2 ) 2 FeMe 2 with 4.0 equiv of 1-Phenyl-1-propyne. In a glove box, a glass vessel was charged with (IEt 2 Me 2 ) 2 FeMe 2 (0.078 g, 0.20 mmol), 1-phenyl-1-propyne (0.094 g, 0.80 mmol), n-dodecane (0.034 g, 0.20 mmol), THF (4.0 ml) and a stir bar. The mixture was stirred at room temperature and followed by GC. During the course of the reaction, the solution slowly turned from light yellow to orange. After 12 h, the mixture was quenched with H 2 O (1 ml). GC analyses indicated the formations of 1a and 2 in 0.05 mmol (13% relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), mmol (1%, relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), respectively. The GC spectrum is shown in Figure S89. The Reaction of (IEt 2 Me 2 ) 2 FeMe 2 with 4.0 equiv of 1-Phenyl-1-propyne in the Presence of 1.0 equiv of MgBr 2. In a glove box, a solution of MgBr 2 Et 2 O (0.052 g, 0.20 mmol) in THF (4.0 ml) was added (IEt 2 Me 2 ) 2 FeMe 2 (0.078 g, 0.20 mmol), 1-phenyl-1-propyne (0.094 g, 0.80 mmol), and n-dodecane (0.034 g, 0.20 mmol) at room temperature. The mixture was stirred and followed by GC. During the course of the reaction, the solution turned from light yellow to orange quickly. After 15 min, the mixture was quenched with H 2 O (1 ml). GC analyses indicated the formations of 1a and 2 in 0.28 mmol (70% relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), mmol (24%, relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), S18

19 respectively. The GC spectrum is shown in Figure S90. Quenching Experiment with D 2 O for the Reaction of (IEt 2 Me 2 ) 2 FeMe 2 with 4.0 equiv of 1-Phenyl-1-propyne and 1.0 equiv of MgBr 2. In a glove box, a solution of MgBr 2 Et 2 O (0.052 g, 0.20 mmol) in THF (4 ml) was added (IEt 2 Me 2 ) 2 FeMe 2 (0.078 g, 0.20 mmol), 1-phenyl-1-propyne (0.094 g, 0.80 mmol), and n-dodecane (0.034 g, 0.20 mmol) at room temperature. The mixture was stirred and followed by GC. During the course of the reaction, the solution turned from light yellow to orange quickly. After 15 min, the mixture was quenched with D 2 O (0.3 ml). GC analyses indicated the formations of 1a-D and 2-D in 0.27 mmol (68% relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), mmol (23%, relative to the methyl anions in (IEt 2 Me 2 ) 2 FeMe 2 ), respectively. The GC and 1 H NMR spectra are shown in Figures S91, S67 and S68, respectively. The Reaction of 1-Phenyl-1-propyne with MeMgBr Catalyzed by (IEt 2 Me 2 ) 2 FeMe 2. In a glove box, a glass vessel was charged with (IEt 2 Me 2 ) 2 FeMe 2 (0.020 g, mmol), n-dodecane (0.085 g, 0.50 mmol), THF (0.50 ml), 1-phenyl-1-proyne (0.116 g, 1.00 mmol), and a stir bar. To the solution was added MeMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol). With vigorous stirring, the color of the solution changed to red brown quickly. After stirred for 15 min at room temperature, the resulting reaction mixture was quenched with water, and analyzed by GC (Figure S92), which indicated the formation of 1a in 82% yield. The Reaction of 1-Phenyl-1-propyne with MeMgBr Catalyzed by IEt 2 Me 2 /FeCl 2. In a glove box, a glass vessel was charged with IEt 2 Me 2 (0.008 g, mmol), FeCl 2 (0.006 g, mmol), THF (0.50 ml) and a stir bar. The mixture was stirred for 10 min at room temperature. To the solution was then added 1-phenyl-1-propyne (0.116 g, 1.00 mmol), n-dodecane (0.085 g, 0.50 mmol), and MeMgBr (1.4 M in THF/toluene, 0.50 ml, 0.70 mmol). The obvious color change from colorless to dark brown was observed immediately. After stirred for 15 min, the resulting reaction mixture was quenched with water, and analyzed by GC-FID, which indicated the formation of 1a in 90% yield (Figure S93). S19

20 References 1. Xiang, L.; Xiao, J.; Deng, L. Organometallics 2011, 30, Przyojski, J. A.; Arman, H. D.; Tonzetich, Z. J. Organometallics 2012, 31, Sherry, B. D.; Fürstner, A. Chem. Commun. 2009, Weiss, H. M.; Touchette, K. M.; Angell, S.; Khan, J. Org. Biomol. Chem. 2003, 1, Cahiez, G.; Gager, O.; Buendia, J. Angew. Chem. Int. Ed. 2010, 49, Khairallah, G. N.; Williams, C. M.; Chow, S.; O Hair, R. A. Dalton Trans. 2013, 42, Zeng, Q.; Zhang, L.; Li, Z.; Qin, J.; Tang, B. Z. Polymer 2009, 50, Sheldrick, G. M. SADABS: Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen: Germany, Sheldrick, G. M. SHELXTL 5.10 for windows NT: Structure Determination Software Programs. Bruker Analytical X-ray systems, Inc.: Madison, Wisconsin, USA, Norambuena, V. F. Q.; Heeres, A.; Heeres, H. J.; Meetsma, A.; Teuben, J. H.; Hessen, B. Organometallics 2008, 27, Aitken, R. A.; Atherton, J. I. J. Chem. Soc., Perkin Trans. 1994, Masuda, T.; Takahashi, T.; Higashimura, T. Macromolecules 1985, 18, S20

21 Table S1. Crystal Data and Summary of Data Collection and Refinement for 5 and 15 a 5 15 Temperature, K 130 K K formula C 27 H 25 NO 4 C 29 H 35 I fw crystal system Orthorhombic Monoclinic space group P n a 21 P 21/c a, Å (5) (18) b, Å (3) (9) c, Å (14) (2) α, deg β, deg (2) γ, deg V, Å (8) (5) Z 4 4 dcalcd, g/cm θ range, deg to to GOF (F 2 ) R1 b , d e , d e WR2 c , d e , d e a Collected using Mo Kα radiation (λ = Å). b R1 = Σ[(Fo Fc)] / Σ(Fo). c wr2 = {Σ[w(Fo2 -Fc2)2 / Σ[w(Fo2)2]]½. d I > 2σ(I). e All data. S21