Gold(I) Catalyzed Intra and Intermolecular Alkenylations of β Yne Pyrroles: Facile Formation of Fused Cycloheptapyrroles and Functionalized Pyrroles Bin Pan, Xiaodong Lu, Chunxiang Wang, Yancheng Hu, Fan Wu, and Boshun Wan* Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China. E-mail: bswan@dicp.ac.cn Supporting Information 1
Table of Contents 1. General information... 3 2. Experiment Procedures and Characterization Data... 3 2.1 The Preparation of β yne pyrroles... 3 2.2 General Procedure for Gold(I) Catalyzed Intramolecular Alkenylations of β Yne Pyrroles... 5 2.3 General Procedure for Gold(I) Catalyzed Intermolecular Alkenylations of Alkynes with β Yne Pyrroles... 9 2.4 Reference... 11 3. Copy of MR Spectra... 12 4. Copy of X ray of 2n... 39 2
1. General information Gold salt and i(cod) 2 was ordered from Aldrich. 2-Methyleneaziridines 4 1-4 were prepared according to literature procedures. Diynes 5-10 were prepared according to literature procedures. β-yne-pyrroles were prepared according to literature procedures 11. Commercially available reagents were used throughout without further purification. All solvents were purified according to the standard procedures. All reactions were carried out under an atmosphere of argon using standard Schlenk techniques, unless otherwise noted. 1 H MR and 13 C MR spectra were recorded on Bruker DRX 400 or Bruker DRX 500 spectrometers (400 MHz or 500 MHz for 1 H MR, 100 MHz or 126 MHz for 13 C MR, see details of each compound) using CDCl 3, CD 3 COCD 3 or C 6 D 6 as solvent. Tetramethylsilane (δ = 0), CDCl 3 (7.27 ppm), CD 3 COCD 3 (2.05 ppm) or C 6 D 6 (7.16 ppm) serves as the internal standard for 1 H MR and CDCl 3 (77.16 ppm), CD 3 COCD 3 (29.84 ppm) or C 6 D 6 (128.06 ppm) for 13 C MR. Coupling constants (J) are reported in Hz and refer to apparent peak multiplications. hromatography was performed on silica gel (300 400 mesh). TLC analysis was performed using glass-backed plates coated with 0.2 mm silica. 2. Experiment Procedures and Characterization Data 2.1 The Preparation of β yne pyrroles General Method: Under an argon atmosphere, 2-Methyleneaziridines 4 (2 eq.), dyines 5 (1 eq.), i(cod) 2 (10 mol % of dyines) and 1,4-dioxane (0.25M) were added into a Schlenk tube. The reaction mixture was stirred at room temperature and monitored by TLC or GC. When the reaction was over, the solvent was removed under reduced pressure and the residue was purified by a flash column chromatography. Experimental Data for β-yne-pyrroles: 3
Colorless oil 1 H MR (500 MHz, CDCl 3 ) δ 7.31 7.25 (m, 2H), 7.20 (t, J = 7.3 Hz, 1H), 6.90 (d, J = 7.3 Hz, 2H), 6.46 (s, 1H), 5.18 (q, J = 7.0 Hz, 1H), 3.72 (s, 3H), 3.66 (s, 3H), 3.27 3.18 (m, 2H), 2.77 2.65 (m, 2H), 1.93 (d, J = 3.1 Hz, 6H), 1.79 (t, J = 2.5 Hz, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13 C MR (126 MHz, CDCl 3 ) δ 171.1, 144.0, 128.6, 126.9, 125.6, 124.9, 115.1, 114.9, 114.7, 78.8, 74.4, 58.9, 54.7, 52.4, 52.4, 27.6, 22.7, 22.4, 9.9, 9.2, 3.5; HRMS calcd for C 24 H 29 O 4 a [M+a] + 418.1994, found 418.19 Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 6.27 (s, 1H), 4.29 (t, J = 5.3 Hz, 1H), 3.77 (d, J = 5.3 Hz, 2H), 3.68 (s, 6H), 3.27 (s, 6H), 3.14 (s, 2H), 2.64 (d, J = 2.5 Hz, 2H), 2.06 (s, 3H), 1.86 (s, 3H), 1.75 (t, J = 2.5 Hz, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 170.8, 124.4, 118.6, 114.8, 114.5, 104.5, 78.6, 74.8, 58.4, 54.9, 52.2, 49.1, 27.2, 22.5, 9.7, 9.1, 3.3; HRMS calcd for C 20 H 29 O 6 a [M+a] + 402.1893, found 402.1889. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.78 (d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 6.82 (d, J = 8.7 Hz, 2H), 6.50 (s, 1H), 4.86 (s, 2H), 4.17 (s, 2H), 3.90 (d, J = 2.3 Hz, 2H), 3.77 (s, 3H), 2.42 (s, 3H), 2.00 (s, 6H), 1.48 (t, J = 2.2 Hz, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 158.8, 142.8, 136.3, 130.4, 128.9, 128.1, 127.5, 125.5, 120.1, 115.1, 114.4, 114.0, 81.1, 72.0, 55.2, 49.9, 41.7, 35.2, 21.4, 9.5, 9.1, 3.1; HRMS calcd for C 26 H 30 2 O 3 a [M+a] + 473.1875, found 473.1874. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.33 7.17 (m, 3H), 6.96 (d, J = 7.1 Hz, 2H), 6.27 (s, 1H), 4.91 (s, 2H), 2.79 (s, 2H), 2.64 (dd, J = 4.7, 2.3 Hz, 2H), 2.42 (q, J = 14.9 Hz, 4H), 1.99 (s, 3H), 1.82 (s, 3H), 1.63 (t, J = 2.4 Hz, 3H), 0.97 (s, 3H), 0.92 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 209.8, 138.4, 128.7, 127.3, 126.3, 125.0, 119.4, 114.9, 76.6, 68.9, 53.43, 50.43, 35.90, 30.74, 30.24, 26.91, 23.13, 9.77, 9.44, 3.41.; HRMS calcd for C 26 H 31 O 2 [M+H] + 389.2355, found 389.2365. 4
Light yellow oil 1 H MR (400 MHz, CDCl 3 ) δ 7.44 7.31 (m, 2H), 7.32 7.22 (m, 3H), 6.85 (dd, J = 22.2, 8.6 Hz, 4H), 6.32 (s, 1H), 4.85 (s, 2H), 3.75 (s, 3H), 3.71 (s, 6H), 3.29 (s, 2H), 2.98 (s, 2H), 1.98 (d, J = 10.9 Hz, 6H); 13 C MR (101 MHz, CDCl 3 ) δ 170.9, 158.9, 131.7, 130.6, 128.2, 127.9, 127.7, 124.7, 123.5, 118.7, 115.2, 114.7, 114.1, 85.6, 83.6, 59.0, 55.3, 52.5, 49.9, 27.8, 23.4, 9.8, 9.4; HRMS calcd for C 29 H 32 O 5 [M+H] + 474.2280, found 474.2298. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 6.85 (q, J = 8.8 Hz, 4H), 6.31 (s, 1H), 4.85 (s, 2H), 3.76 (s, 3H), 3.69 (s, 6H), 3.22 (s, 2H), 2.77 (d, J = 2.6 Hz, 2H), 2.04 (t, J = 2.6 Hz, 1H), 1.98 (s, 3H), 1.92 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 170.7, 158.9, 130.7, 127.6, 124.7, 118.7, 115.1, 114.6, 114.1, 80.0, 71.4, 58.6, 55.3, 52.5, 49.9, 27.6, 22.5, 9.7, 9.4; HRMS calcd for C 23 H 27 O 5 a [M+a] + 420.1787, found 420.1776. 2.2 General Procedure for Gold(I) Catalyzed Intramolecular Alkenylations of β Yne Pyrroles Under an argon atmosphere, a solution of β-yne-pyrrole and [JohnPhosAu(CMe)]SbF 6 (5mol%) in anhydrous toluene (or dichloromethane) was stirred at room temperature. When TLC indicated the disappearance of the starting material, the reaction mixture was concentrated and purified by a flash column chromatography on silica gel to afford the corresponding product. Experimental Data for Products MeO 2a Colorless oil, 1 H MR (500 MHz, Acetone) δ 6.88 6.78 (m, 4H), 5.77 (t, J = 7.0 Hz, 1H), 5.04 (s, 2H), 3.74 (s, 3H), 3.68 (s, 6H), 2.79 (s, 2H), 2.32 (d, J = 7.0 Hz, 2H), 2.02 (s, 3H), 2.00 (s, 3H), 1.90 (s, 3H); 13 C MR (126 MHz, Acetone) δ 172.6, 159.7, 133.8, 5
132.2, 130.9, 127.6, 126.4, 125.1, 120.4, 114.7, 114.5, 71.1, 55.5, 52.6, 48.1, 33.7, 21.9, 10.0, 9.4; HRMS calcd for C 24 H 29 O 5 a [M+a] + 434.1943, found 434.1956. Colorless oil, 1 H MR (400 MHz, CDCl 3 ) δ 7.16 (t, J = 7.9 Hz, 1H), 6.72 (dd, J = 8.1, 2.1 Hz, 1H), 6.50 (d, J = 7.6 Hz, 1H), 6.39 (s, 1H), 5.83 (t, J = 7.1 Hz, 1H), 5.00 (s, 2H), 3.71 (s, 6H), 3.70 (s, 3H), 2.83 (s, 2H), 2.35 (d, J = 7.1 Hz, 2H), 2.04 (s, 3H), 2.02 (s, 3H),1.89 (s, 3H); 13 C MR (126 MHz, Acetone) δ 172.2, 159.8, 140.6, 132.7, 130.3, 129.4, 125.8, 124.6, 119.5, 117.8, 114.1, 112.3, 111.0,70.2, 54.9, 52.2, 48.0, 32.8, 28.7, 21.5, 9.8, 9.0; HRMS calcd for C 24 H 29 O 5 a [M+a] + 434.1943, found 434.1956. Colorless oil, 1 H MR (500 MHz, CDCl 3 ) δ 7.21 7.18 (m, 1H), 6.90 6.76 (m, 2H), 6.42 6.35 (m, 1H), 5.81 (td, J = 7.1, 1.5 Hz, 1H), 5.00 (s, 2H), 3.87 (s, 3H), 3.74 (s, 6H), 2.85 (s, 2H), 2.36 (d, J = 6.9 Hz, 2H), 2.09 (s, 3H), 2.03 (s, 3H), 1.84 1.78 (m, 3H), 1.59 (s, 3H); 13 C MR (126 MHz, CDCl 3 ) δ 172.5, 155.8, 133.0, 130.5, 127.7, 127.3, 126.3, 125.9, 124.4, 120.7, 119.4, 113.9, 109.4, 70.4, 55.2, 52.4, 43.6, 32.9, 28.9, 21.6, 9.7, 9.2; HRMS calcd for C 24 H 29 O 5 a [M+a] + 434.1943, found 434.1937. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ7.31 7.20 (m, 3H), 7.05 (d, J = 7.9 Hz, 2H), 5.93 (dt, J = 7.0, 3.5 Hz, 1H), 5.44 (q, J = 7.2 Hz, 1H), 3.74 (s, 3H), 3.73 (s, 3H), 2.93 (d, J = 14.1 Hz, 1H), 2.75 (d, J = 14.1 Hz, 1H), 2.51 2.37 (m, 2H), 1.98 (s, 3H), 1.96 (s, 3H), 1.83 (d, J = 7.2 Hz, 3H), 1.79 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 172.4, 172.3, 142.5, 132.8, 131.4, 128.4, 126.7, 126.0, 125.5, 125.4, 118.6, 115.4, 69.9, 53.6, 52.4, 52.4, 32.9, 28.8, 22.2, 19.4, 11.5, 8.9; HRMS calcd for C 24 H 29 O 4 a [M+a] + 418.1994, found 418.1985. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 5.92 (t, J = 7.1 Hz, 1H), 3.84 (dd, J = 19.6, 7.7 Hz, 1H), 3.71 (s, 6H), 2.77 (s, 2H), 2.35 (d, J = 7.0 Hz, 2H), 2.26 (s, 3H), 2.03 (s, 3H), 2.00 (s, 3H), 1.96 1.79 (m, 6H), 1.40 1.14 (m, 4H); 13 C MR (101 MHz, 6
CDCl 3 ) δ 172.4 133.1, 130.8, 125.3, 125.0, 118.2, 115.1, 69.8, 57.7, 52.4, 32.8, 32.6, 28.8, 26.7, 25.6, 22.5, 12.4, 9.0; HRMS calcd for C 22 H 31 O 4 a [M+a] + 396.2151, found 396.2159. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 5.86 (t, J = 6.9 Hz, 1H), 4.27 (t, J = 5.2 Hz, 1H), 3.92 (d, J = 5.2 Hz, 2H), 3.69 (s, 6H), 3.23 (s, 6H), 2.78 (s, 2H), 2.32 (d, J = 7.0 Hz, 2H), 2.14 (s, 3H), 2.02 (s, 3H), 1.99 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 172.2, 132.8, 129.9, 126.2, 124.5, 119.8, 113.8, 104.7, 70.2, 55.2, 52.2, 47.7, 32.8, 28.6, 21.4, 10.1, 9.0; HRMS calcd for C 20 H 29 O 6 a [M+a] + 402.1893, found 402.1898. Colorless oil, 1 H MR (400 MHz, CDCl 3 ) δ 7.23 (m, 3H), 6.90 (d, J = 7.3 Hz, 2H), 5.83 (td, J = 7.0, 1.3 Hz, 1H), 5.04 (s, 2H), 3.73 (s, 6H), 2.85 (s, 2H), 2.35 (d, J = 7.1 Hz, 2H), 2.07 (s, 3H), 2.03 (s, 3H), 1.88 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 172.3, 138.8, 132.6, 130.3, 128.4, 126.7, 125.7, 125.5, 124.7, 119.5, 114.0, 70.2, 52.3, 48.0, 32.8, 28.7, 21.6, 9.8, 9.1; HRMS calcd for C 23 H 27 O 4 a [M+a] + 404.1838, found 404.1850. Bn 2h CO 2 Et CO 2 Et Colorless oil 1 H MR (500 MHz, CDCl 3 ) δ 7.30 7.17 (m, 3H), 6.90 (d, J = 7.1 Hz, 2H), 5.83 (td, J = 7.1, 1.4 Hz, 1H), 5.05 (s, 2H), 4.19 (qd, J = 7.1, 1.5 Hz, 4H), 2.85 (s, 2H), 2.35 (d, J = 7.0 Hz, 2H), 2.07 (s, 3H), 2.03 (s, 3H), 1.88 (s, 3H), 1.26 (t, J = 7.1 Hz, 6H); 13 C MR (126 MHz, CDCl 3 ) δ 172.0, 139.0, 132.6, 130.5, 128.5, 126.9, 125. 8, 125.6, 125.0, 119.7, 114.1, 70.5, 61.1, 48.2, 32.9, 28.7, 21.7, 14.1, 10.0, 9.3; HRMS calcd for C 25 H 31 O 4 a [M+a] + 432.2151, found 432.2157. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.36 7.16 (m, 15H), 6.89 (d, J = 7.0 Hz, 2H), 5.80 (td, J = 7.0, 1.4 Hz, 1H), 5.13 (s, 4H), 5.05 (s, 2H), 2.90 (s, 2H), 2.42 (d, J = 7.1 Hz, 2H), 2.03 (s, 3H), 1.98 (s, 3H), 1.89 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 171.5, 138.8, 135.6, 132.7, 130.3, 128.4, 128.3, 127.9, 127.7, 126.7, 125.7, 125.4, 124.5, 119.4, 114.0, 70.5, 66.6, 48.0, 32.8, 28.7, 21.5, 9.8, 9.0; HRMS calcd for C 35 H 35 O 4 a [M+a] + 556.2464, found 556.2469. 7
White solid, m.p.77-78, 1 H MR (400 MHz, C 6 D 6 ) δ 6.74 (d, J = 8.6 Hz, 2H), 6.66 (d, J = 8.7 Hz, 2H), 5.90 (t, J = 7.0 Hz, 1H), 4.76 (s, 2H), 3.24 (s, 3H), 2.52 (t, J = 7.2 Hz, 2H), 2.18 2.10 (m, 2H), 2.09 (s, 3H), 2.07 2.00 (m, 2H), 1.97 1.92 (m, 6H); 13 C MR (101 MHz, C 6 D 6 ) δ 158.8, 131.5, 131.1, 130.2, 128.2, 126.7, 124.9, 123.2, 113.9, 113.0, 54.3, 47.4, 36.5, 26.5, 22.2, 22.0, 9.7, 9.3; HRMS calcd for C 20 H 26 O [M+H] + 296.2014, found 296.2019. White solid, m.p.55-56, 1 H MR (400 MHz, CDCl 3 ) δ 7.69 (d, J = 8.2 Hz, 2H), 7.25 (d, J = 8.1 Hz, 3H), 6.73 (d, J = 8.7 Hz, 2H), 6.65 (d, J = 8.6 Hz, 2H), 5.50 (td, J = 7.3, 0.8 Hz, 1H), 4.93 (s, 2H), 3.98 (s, 2H), 3.73 (s, 3H), 3.49 (d, J = 7.4 Hz, 2H), 2.39 (s, 3H), 1.99 (s, 3H), 1.92 (s, 3H), 1.83 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 158.7, 142.8, 136.9, 136.0, 131.4, 130.4, 129.4, 127.6, 127.5, 126.5, 121.7, 118.4, 114.0, 113.5, 55.2, 47.6, 44.2, 41.5, 21.5, 21.1, 9.9, 9.2; HRMS calcd for C 26 H 30 2 O 3 as [M+a] + 473.1875, found 473.1884. White solid, m.p.91-92, 1 H MR (400 MHz, Acetone) δ 6.84 (d, J = 8.7 Hz, 2H), 6.78 (d, J = 8.7 Hz, 2H), 5.86 (td, J = 7.0, 1.1 Hz, 1H), 5.08 (s, 2H), 4.06 (s, 2H), 3.69 (s, 3H), 3.49 (d, J = 7.0 Hz, 2H), 2.05 (s, 3H), 1.99 (s, 3H), 1.96 (s, 3H); 13 C MR (101 MHz, Acetone) δ 163.4, 141.7, 137.1, 135.9, 132.7, 131.8, 130.0, 127.6, 119.2, 117.4, 66.4, 64.3, 60.2, 52.1, 26.1, 15.0, 14.1; HRMS calcd for C 19 H 24 O 2 [M+H] + 298.1807, found 298.1803. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.27 7.16 (m, 3H), 6.86 (d, J = 7.5 Hz, 2H), 5.77 (t, J = 7.1 Hz, 1H), 5.01 (s, 2H), 2.78 (s, 1H), 2.76 (s, 2H), 2.75 (s, 1H), 2.52 (d, J = 14.1 Hz, 2H), 2.24 (d, J = 7.1 Hz, 2H), 1.97 (d, J = 7.3 Hz, 6H), 1.84 (s, 3H), 1.06 (s, 3H), 0.89 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 207.6, 138.8, 131.4, 130.6, 128.4, 126.7, 126.0, 125.6, 125.4, 118.1, 113.6, 83.8, 51.3, 48.0, 30.6, 30.4, 30.0, 29.1, 27.6, 21.4, 9.7, 9.2; HRMS calcd for C 26 H 31 O 2 a [M+a] + 412.2252, found 412.2249. 8
White solid, m.p.158-159, 1 H MR (400 MHz, CDCl 3 ) δ 7.26 7.14 (m, 5H), 6.69 (d, J = 8.6 Hz, 2H), 6.56 (d, J = 8.5 Hz, 2H), 6.15 (t, J = 7.2 Hz, 1H), 4.44 (s, 2H), 3.72 (s, 9H), 2.95 (s, 2H), 2.51 (d, J = 7.2 Hz, 2H), 2.09 (s, 3H), 2.07 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 172.0, 158.3, 140.5, 138.4, 131.0, 128.1, 127.5, 127.3, 127.1, 126.9, 126.2, 125.8, 121.7, 114.1, 113.6, 77.2, 76.8, 76.5, 70.8, 55.0, 52.2, 47.2, 33.3, 28.6, 10.0, 9.0; HRMS calcd for C 29 H 31 O 5 a [M+a] + 496.2100, found 496.2105. White solid, m.p.93-94, 1 H MR (400 MHz, C 6 D 6 ) δ 6.67 (d, J = 8.7 Hz, 2H), 6.59 (d, J = 8.7 Hz, 2H), 4.81 (s, 1H), 4.79 (s, 2H), 4.66 (s, 1H), 3.32 (s, 2H), 3.27 (s, 6H), 3.21 (s, 2H), 3.16 (s, 3H), 1.89 (s, 3H), 1.76 (s, 3H); 13 C MR (101 MHz, C 6 D 6 ) δ 171.1, 158.8, 132.8, 130.3, 128.8, 126.7, 125.1, 119.4, 114.1, 112.8, 103.5, 55.9, 54.3, 51.8, 47.4, 40.7, 29.2, 9.2, 8.9; HRMS calcd for C 23 H 27 O 5 a [M+a] + 420.1787, found 420.1789. 2.3 General Procedure for Gold(I) Catalyzed Intermolecular Alkenylations of Alkynes with β Yne Pyrroles Under an argon atmosphere, a solution of β-yne-pyrrole (1 eq.), alkyne (1 eq.) and [JohnPhosAu(CMe)]SbF 6 (5mol%) in anhydrous toluene was stirred at room temperature. When TLC indicated the disappearance of the starting material, the reaction mixture was concentrated and purified by a flash column chromatography on silica gel to afford the corresponding product. Experimental Data for Products Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.23 7.20 (m, 5H), 6.71 (d, J = 8.7 Hz, 2H), 6.63 (d, J = 8.6 Hz, 2H), 5.74 (d, J = 1.2 Hz, 1H), 5.18 (d, J = 1.1 Hz, 1H), 4.61 (s, 2H), 3.72 (s, 3H), 3.56 (s, 6H), 3.20 (s, 2H), 2.63 (d, J = 2.4 Hz, 2H), 1.95 (s, 3H), 1.94 (s, 3H), 1.60 (t, J = 2.3 Hz, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 171.1, 158.2, 140.4, 139.5, 131.3, 130.2, 127.9, 127.5, 126.8, 9
126.5, 125.2, 118.1, 115.1, 114.5, 113.6, 78.1, 74.8, 58.7, 55.0, 52.0, 47.0, 26.8, 23.3, 10.2, 9.7, 3.3; HRMS calcd for C 32 H 35 O 5 a [M+a] + 536.2413, found 536.2427. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.11 (d, J = 8.7 Hz, 2H), 6.71 6.55 (m, 6H), 5.58 (s, 1H), 5.02 (s, 1H), 4.57 (s, 2H), 3.69 (s, 3H), 3.64 (s, 3H), 3.50 (s, 6H), 3.17 (s, 2H), 2.57 (d, J = 2.1 Hz, 2H), 1.89 (d, 6H), 1.56 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 171.3, 159.3, 158.4, 139.2, 133.3, 131.5, 130.7, 128.0, 127.0, 125.3, 116.3, 115.2, 114.5, 113.8, 113.5, 78.2, 75.1, 59.0, 55.2, 52.2, 47.2, 27.0, 23.5, 10.3, 9.9, 3.5; HRMS calcd for C 33 H 37 O 6 a [M+a] + 566.2519, found 566.2531. Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.17 (d, J = 8.7 Hz, 2H), 6.77 (d, J = 8.8 Hz, 2H), 6.72 (d, J = 2.7 Hz, 4H), 5.60 (d, J = 1.6 Hz, 1H), 5.09 (d, J = 1.5 Hz, 1H), 4.65 (s, 2H), 3.77 (s, 3H), 3.73 (s, 3H), 2.50 2.39 (m, 2H), 2.10 2.05 (m, 2H), 2.04 (s, 3H), 2.02 (s, 3H), 1.74 (t, J = 2.3 Hz, 3H), 1.68 1.56 (m, 2H); 13 C MR (101 MHz, CDCl 3 ) δ 159.1, 158.1, 139.8, 133.8, 131.5, 129.0, 127.8, 127.0, 124.9, 120.9, 115.7, 113.6, 113.6, 113.4, 79.4, 75.2, 55.1, 55.0, 47.0, 30.9, 24.4, 18.7, 10.0, 9.5, 3.3; HRMS calcd for C 29 H 34 O 2 [M+H] + 428.2590, found 428.2600. Light yellow oil, 1 H MR (400 MHz, CDCl 3 ) δ 6.79 (d, J = 8.6 Hz, 2H), 6.71 (d, J = 8.5 Hz, 2H), 5.56 (s, 1H), 5.06 (s, 1H), 4.91 (s, 2H), 4.10 (s, 2H), 3.75 (s, 3H), 3.67 (s, 6H), 3.29 (s, 2H), 2.69 (d, J = 2.0 Hz, 2H), 1.95 (s, 3H), 1.92 (s, 3H), 1.75 (s, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 171.1, 158.3, 141.3, 131.2, 128.4, 126.4, 125.3, 117.3, 115.0, 113.8, 113.4, 78.5, 75.1, 65.2, 58.7, 55.0, 52.3, 46.7, 27.1, 23.3, 10.0, 9.4, 3.3; HRMS calcd for C 27 H 34 O 6 [M+H] + 468.2386, found 468.2383. White solid, m.p.147-148, 1 H MR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 16.2 Hz, 1H), 6.82 (q, J = 8.8 Hz, 4H), 5.66 (d, J = 16.2 Hz, 1H), 5.14 (s, 2H), 3.78 (s, 3H), 3.66 (s, 9H), 3.40 (s, 2H), 2.65 (d, J = 2.5 Hz, 2H), 2.06 (s, 3H), 2.01 (s, 3H), 1.81 (t, J = 2.4 Hz, 3H); 13 C MR (101 MHz, CDCl 3 ) δ 170.7, 168.6, 158.8, 133.4, 132.0, 129.2, 126.7, 125.9, 123.8, 117.8, 114.4, 109.1, 79.5, 10
77.3, 77.0, 76.7, 74.4, 59.1, 55.3, 52.5, 51.1, 48.0, 26.7, 23.2, 10.3, 10.0, 3.5; HRMS calcd for C 28 H 34 O 7 [M+H] + 496.2329, found 496.2330. 2.4 Reference (1) Bhat, L.; Steinig, A. G.; Appelbe, R.; Meijere, A. Eur. J. Org. Chem. 2001, 1673. (2) Ince, J.; Ross, T. M.; Shipman, M; Slawin, A. M. Z. Tetrahedron. 1996, 52, 7037. (3) Shiers, J. J.; Shipman, M; Hayes, J. F.; Slawin, A. M. Z. J. Am. Chem. Soc. 2004, 126, 6868. (4) Kimpe,. D.; Smaele, D. D.; Sakonyi, Z. J. Org. Chem. 1997, 62, 2448. (5) Tanaka, K.; Takeishi, K.; oguchi, K.; J. Am. Chem. Soc. 2006, 128, 4586. (6) Takimoto, M.; Mizuno, T.; Morib, M.; Sato, Y. Tetrahedron. 2006, 62, 7589. (7) Sperger, C.; Strand, L.H.S.; Fiksdahl, A.; Tetrahedron. 2010, 66, 7749. (8) Ishizaki, M.; Hoshino, O. Tetrahedron. 2000, 56, 8813. (9) Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2007, 129, 13402. (10) Wender, P. A.; Christy, J. P.; Lesser, A. B.; Gieseler, M. T. Angew. Chem. Int. Ed. 2009, 48, 7687. (11) Pan, B.; Wang, C. X.; Wang, D. P.; Wu, F.; Wan, B. S. Chem. Commun. 2013, 49, 5073. 11
3. Copy of MR Spectra Ph 1d Ph 1d 12
MeO OMe 1f MeO OMe 1f 13
PMB Ts 1k PMB Ts 1k 14
O Bn O 1m O Bn O 1m 15
PMB Ph 1n PMB Ph 1n 16
PMB H 1p PMB H 1p 17
PMB 2a PMB 2a 18
PMB 2a 19
MeO 2b 172.2 159.8 140.6 132.7 130.3 129.4 125.8 124.6 119.5 117.8 114.1 112.3 111.0 70.2 54.9 52.2 48.0 32.8 28.7 21.5 9.8 9.0 MeO 2b 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 20
OMe 2c OMe 2c 21
2d 2d 22
2e 2e 23
MeO MeO 2f 172.2 132.8 129.9 126.2 124.5 119.8 113.8 104.7 70.2 55.2 52.2 47.7 32.8 28.6 21.4 10.1 9.0 MeO MeO 2f 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 24
Bn 2g Bn 2g 25
26 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 f1 (ppm) 6.11 3.01 3.05 3.05 2.04 2.02 4.08 2.00 1.00 1.97 3.29 1.24 1.26 1.27 1.88 2.03 2.07 2.34 2.36 2.85 4.17 4.17 4.18 4.19 4.20 4.20 4.21 4.21 5.05 5.81 5.81 5.83 5.83 5.84 5.84 6.89 6.90 7.20 7.25 7.25 7.26 7.28 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 80 f1 (ppm) 9.3 10.0 14.1 21.7 28.7 32.9 48.2 61.1 70.5 114.1 119.7 125.0 125.6 125.8 126.9 128.5 130.5 132.6 139.0 172.0 Bn CO 2 Et CO 2 Et 2h Bn CO 2 Et CO 2 Et 2h
Bn CO 2 Bn CO 2 Bn 2i Bn CO 2 Bn CO 2 Bn 2i 27
PMB 2j PMB 2j 28
PMB Ts 2k PMB Ts 2k 29
PMB O 2l PMB O 2l 30
Bn O O 2m Bn O O 2m 31
Ph PMB 2n 172.0 158.3 140.5 138.4 128.1 127.3 127.1 126.9 125.8 114.1 113.6 77.2 76.8 76.5 70.8 55.0 52.2 47.2 33.3 28.6 10.0 9.1 Ph PMB 2n 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 32
PMB 2p PMB 2p 33
PMB Ph X Me X=C() 2 3a PMB Ph X Me X=C() 2 3a 34
PMB PMP X Me X=C() 2 3b 171.3 159.3 158.4 139.2 133.3 131.5 130.7 128.0 127.0 125.3 116.3 115.2 114.5 113.8 113.5 78.2 75.1 59.0 55.2 52.2 47.2 27.0 23.5 10.3 9.9 3.5 PMB PMP X Me X=C() 2 3b 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 35
PMB PMP Me 3c PMB PMP Me 3c 36
PMB X OH Me X=C() 2 3d PMB X OH Me X=C() 2 3d 37
PMB X Me X=C() 2 3e PMB X Me X=C() 2 3e 38
4. Copy of X-ray of 2n 39