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1 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 , China. Supporting Information 1

2 Table of Contents 1. General information Experiment Procedures and Characterization Data The Preparation of β yne pyrroles General Procedure for Gold(I) Catalyzed Intramolecular Alkenylations of β Yne Pyrroles General Procedure for Gold(I) Catalyzed Intermolecular Alkenylations of Alkynes with β Yne Pyrroles Reference Copy of MR Spectra Copy of X ray of 2n

3 1. General information Gold salt and i(cod) 2 was ordered from Aldrich. 2-Methyleneaziridines 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 ( ppm) for 13 C MR. Coupling constants (J) are reported in Hz and refer to apparent peak multiplications. hromatography was performed on silica gel ( 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

4 Colorless oil 1 H MR (500 MHz, CDCl 3 ) δ (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), (m, 2H), (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] , found 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] , found 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] , found Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ (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] , found

5 Light yellow oil 1 H MR (400 MHz, CDCl 3 ) δ (m, 2H), (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] , found 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] , found 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 (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

6 132.2, 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] , found 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] , found Colorless oil, 1 H MR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (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), (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] , found Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ (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), (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] , found 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), (m, 6H), (m, 4H); 13 C MR (101 MHz, 6

7 CDCl 3 ) δ , 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] , found 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] , found 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] , found Bn 2h CO 2 Et CO 2 Et Colorless oil 1 H MR (500 MHz, CDCl 3 ) δ (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, , 125.6, 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] , found Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ (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] , found

8 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), (m, 2H), 2.09 (s, 3H), (m, 2H), (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] , found 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] , found 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] , found Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ (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] , found

9 White solid, m.p , 1 H MR (400 MHz, CDCl 3 ) δ (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] , found 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] , found 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 (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

10 126.5, 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] , found Colorless oil 1 H MR (400 MHz, CDCl 3 ) δ 7.11 (d, J = 8.7 Hz, 2H), (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] , found 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), (m, 2H), (m, 2H), 2.04 (s, 3H), 2.02 (s, 3H), 1.74 (t, J = 2.3 Hz, 3H), (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] , found 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] , found White solid, m.p , 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

11 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] , found Reference (1) Bhat, L.; Steinig, A. G.; Appelbe, R.; Meijere, A. Eur. J. Org. Chem. 2001, (2) Ince, J.; Ross, T. M.; Shipman, M; Slawin, A. M. Z. Tetrahedron. 1996, 52, (3) Shiers, J. J.; Shipman, M; Hayes, J. F.; Slawin, A. M. Z. J. Am. Chem. Soc. 2004, 126, (4) Kimpe,. D.; Smaele, D. D.; Sakonyi, Z. J. Org. Chem. 1997, 62, (5) Tanaka, K.; Takeishi, K.; oguchi, K.; J. Am. Chem. Soc. 2006, 128, (6) Takimoto, M.; Mizuno, T.; Morib, M.; Sato, Y. Tetrahedron. 2006, 62, (7) Sperger, C.; Strand, L.H.S.; Fiksdahl, A.; Tetrahedron. 2010, 66, (8) Ishizaki, M.; Hoshino, O. Tetrahedron. 2000, 56, (9) Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2007, 129, (10) Wender, P. A.; Christy, J. P.; Lesser, A. B.; Gieseler, M. T. Angew. Chem. Int. Ed. 2009, 48, (11) Pan, B.; Wang, C. X.; Wang, D. P.; Wu, F.; Wan, B. S. Chem. Commun. 2013, 49,

12 3. Copy of MR Spectra Ph 1d Ph 1d 12

13 MeO OMe 1f MeO OMe 1f 13

14 PMB Ts 1k PMB Ts 1k 14

15 O Bn O 1m O Bn O 1m 15

16 PMB Ph 1n PMB Ph 1n 16

17 PMB H 1p PMB H 1p 17

18 PMB 2a PMB 2a 18

19 PMB 2a 19

20 MeO 2b MeO 2b f1 (ppm)

21 OMe 2c OMe 2c 21

22 2d 2d 22

23 2e 2e 23

24 MeO MeO 2f MeO MeO 2f f1 (ppm)

25 Bn 2g Bn 2g 25

26 f1 (ppm) f1 (ppm) Bn CO 2 Et CO 2 Et 2h Bn CO 2 Et CO 2 Et 2h

27 Bn CO 2 Bn CO 2 Bn 2i Bn CO 2 Bn CO 2 Bn 2i 27

28 PMB 2j PMB 2j 28

29 PMB Ts 2k PMB Ts 2k 29

30 PMB O 2l PMB O 2l 30

31 Bn O O 2m Bn O O 2m 31

32 Ph PMB 2n Ph PMB 2n f1 (ppm)

33 PMB 2p PMB 2p 33

34 PMB Ph X Me X=C() 2 3a PMB Ph X Me X=C() 2 3a 34

35 PMB PMP X Me X=C() 2 3b PMB PMP X Me X=C() 2 3b f1 (ppm)

36 PMB PMP Me 3c PMB PMP Me 3c 36

37 PMB X OH Me X=C() 2 3d PMB X OH Me X=C() 2 3d 37

38 PMB X Me X=C() 2 3e PMB X Me X=C() 2 3e 38

39 4. Copy of X-ray of 2n 39