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1 Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2017 Catalyst controlled Regioselectivity in Phosphine Catalysis: Synthesis of Spirocyclic Benzofuranones via Regiodivergent [3+2] Annulations of Aurones and an Allenoate Huanzhen Ni, [a][b] Zhaoyuan Yu, [b][c] Weijun Yao, [d] Yu Lan,* [c] Nisar Ullah,* [e] and Yixin Lu* [a][b][f] [a] Graduate School for Integrative Sciences & Engineering (NGS), Centre for Life Sciences (CeLS), National University of Singapore, #05 01, 28 Medical Drive, Singapore [b] Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore. [c] School of Chemistry and Chemical Engineering, Chongqing University, Chongqing , P. R. China. [d] Department of chemistry, Zhejiang Sci Tech University, , P. R. China. [e] Chemistry Department, King Fahd University of Petroleum and Materials, Dhahran 31261, Saudi Arabia. [f] National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Suzhou, Jiangsu, PR China, chmlyx@nus.edu.sg; lanyu@cqu.edu.cn; nullah@kfupm.edu.sa Supporting Information A. General information S2 B. Representative Procedure S2 C. Synthesis of dipeptide phosphine catalysts S3 D. Analytical data and HPLC Chromatogram of the Products S4 E. Synthesis of product 8 S45 F. Determination of stereochemistry of product 8 by 2D NMR S48 G. Computational methods S49 H. Proposed Reaction Cycle and DFT studies S50 I. Calculated Gibbs free energy profiles for the phosphine catalyzed [3+2] S51 annulation of aurone 1a and allene 2a J. B3LYP and M11 absolute calculation energies, enthalpies, and free energies. S55 K. B3LYP geometries for all the optimized compounds and transition states. S57 L. References S114 M. NMR Spectra of the Products S116 S1
2 A. General Information Unless otherwise specified, all reactions were carried out under a nitrogen atmosphere in anhydrous conditions. All the solvents were purified according to the standard procedures. All chemicals which are commercially available were used without further purification unless otherwise noted. Thin layer chromatography (TLC) was performed on silica gel plates (60F 254) using UV light (254 and 365 nm). Flash chromatography was conducted on silica gel ( mesh). 1 H and 13 C NMR spectra were recorded at ambient temperature in CDCl 3 on a Bruker AMX500 (500 MHz) spectrometer. Chemical shifts were reported in parts per million (ppm). All high resolution mass spectra were obtained on a Finnigan/MAT 95XL T spectrometer. ptical rotations were measured using a Jasco DIP 1000 polarimeter. Enantiomeric excesses were determined by HPLC analysis on a chiral stationary phase. Catalyst 3 and 4 were synthesized by following our previously reported procedures. 1 Aurones 1 were synthesized according to literature reported procedures. 2 B. Representative Procedure To a dried round bottle flask with a magnetic stirring bar under N 2 at room temperature were added aurones 1 (0.1 mmol) and allenoate 2a (0.12 mmol), followed by the addition of anhydrous ether (0.5 ml, for selective reaction) or CH 2 Cl 2 (0.5 ml, for selective reaction). Catalyst 4g (0.01 mmol, 10 mg, for selective reaction) or 4b (0.01 mmol, 10 mg, for selective reaction) was then introduced, and the reaction mixture was stirred for 12 hours. The solvent was then removed under reduced pressure and crude product was dissolved in CDCl 3 to for 1 H NMR to analyze the ratio for product 5 and 6. The crude product was then purified by column chromatography (Hexane: ether = 10:1) on silica gel to afford the major annulation adducts 5 or 6. S2
3 C. Synthesis of dipeptide phosphine catalysts Dipeptide catalysts were synthesized according to the previous reported procedure. 1 Catalyst 4c: a white solid; 1 H NMR (500 MHz, acetone d 6 ) δ 8.56 (s, 2H), 8.21 (s, 1H), 7.69 (ddd, J = 7.1 Hz, 5.8 Hz, 1.3 Hz, 4H), (m, 7H), (m, 10H), (m, 1H), 4.14 (qd, J = 6.2 Hz, 2.8 Hz, 1H), 4.07 (ddd, J = 11.6 Hz, 8.9 Hz, 4.5 Hz, 1H), 2.57 (ddd, J = 13.7 Hz, 4.1 Hz, 2.9 Hz, 1H), 2.40 (ddd, J = 13.6 Hz, 10.5Hz, 3.0 Hz, 1H), 2.31 (dq, J = 13.7 Hz, 6.8 Hz, 1H), 1.08 (d, J = 6.7 Hz, 3H), 1.05 (d, J = 6.8 Hz, 3H), 1.02 (s, 9H), 0.94 (d, J = 6.2 Hz, 3H); 13 C NMR (125 MHz, acetone d 6 ) δ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 71.00, 70.93, 59.69, 51.97, 51.84, 30.54, 26.61, 19.44, 19.42, 18.98, 18.46, 18.02; 31 P NMR (202 MHz, acetone d 6 ) δ 22.24; HRMS (ESI) m/z calcd for C 46 H 50 F 6 N 2 3 PSi [M + H] + = , found = Catalyst 4e: a white solid; 1 H NMR (500 MHz, acetone d 6 ) δ 8.60 (s, 2H), (m, 2H), 7.72 (dt, J = 8.0 Hz, 1.2 Hz, 4H), 7.46 (ddd, J = 9.9 Hz, 7.3 Hz, 5.8 Hz, 2H), 7.40 (dd, J = 11.2 Hz, 4.3 Hz, 5H), (m, 10H), 4.59 (dd, J = 8.5 Hz, 7.2 Hz, 1H), 4.16 (qd, J = 6.2 Hz, 2.3 Hz, 1H), (m, 1H), 2.49 (ddd, J = 13.7 Hz, 4.8 Hz, 1.9 Hz, 1H), (m, 2H), 1.01 (m, J = 10.6 Hz, 5.0 Hz, 18H); 13 C NMR (125 MHz, acetone d 6 ) δ , , , , , , , , , , , , , , , , , , , , , , , , , , , , 71.16, 71.10, 59.52, 51.88, 51.75, 30.98, 30.87, 30.57, 26.59, 19.15, 19.13, 18.98, 17.81; 31 P NMR (202 MHz, acetone d 6 ) δ 22.68; HRMS (ESI) m/z calcd for C 46 H 50 F 6 N 2 3 PSi [M + H] + = , found = Catalyst 4g: a white solid; 1 H NMR (500 MHz, acetone d 6 ) δ 8.55 (s, 2H), 8.25 (s, 1H), 8.07 (d, J = 7.6 Hz, 1H), (m, 4H), (m, 2H), (m, 8H), (m, 6H), 7.19 (d, J = 9.1 Hz, 1H), 4.64 (dd, J = 7.6 Hz, 4.2 Hz, 1H), (m, 1H), 4.21 (qd, J = 6.2 Hz, 2.7 Hz, 1H), (m, 1H), 2.59 (dd, J = 13.8 Hz, 4.2 Hz, 1H), 2.30 (ddd, J = 13.7 Hz, 9.8 Hz, 1.8 Hz, 1H), 1.22 (d, J = 6.3 Hz, 3H), (m, 12H), 0.91 (s, 9H), 0.17 (d, J = 7.1 Hz, 6H); 13 C NMR (125 MHz, acetone d 6 ) δ , , , , , , , S3
4 133.97, , , , , , , , , , , , , , , , , , , , 70.66, 70.60, 68.47, 59.09, 52.10, 51.98, 30.21, 30.10, 26.64, 25.46, 19.14, 18.96, 18.74, 17.72, 5.23, 5.36; 31 P NMR (202 MHz, Acetone d 6 ) δ 22.60; HRMS (ESI) m/z calcd for C 51 H 62 F 6 N 2 4 PSi 2 [M + H] + = , found = D. Analytical Data and HPLC Chromatogram of the Products tert Butyl (2R,2'S) 3 oxo 2' phenyl 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5a C 2 tbu A white solid; [α] 25 D = (c 1.0, CHCl 3 ); 1H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 3H), 7.01 (dd, J = 7.4 Hz, 1.7 Hz, 2H), 6.97 (t, J = 7.4 Hz, 1H), 6.93 (q, J = 2.5 Hz, 1H), 6.69 (d, J = 8.4 Hz, 1H), 4.54 (d, J = 1.9 Hz, 1H), 3.16 (dt, J = 18.9 Hz, 2.0 Hz, 1H), 2.90 (ddd, J = 18.9 Hz, 2.5 Hz, 1.5 Hz, 1H), 1.22 (s, 9H). ; 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 95.44, 80.75, 59.82, 41.90, 27.71; HRMS (ESI) m/z calcd for C 23 H 22 Na 4 [M + Na] + = , found = ; The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). racemic 5a S4
5 enantiomeric enriched 5a tert Butyl (2R,2'S) 2' (4 chlorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5b C 2 tbu Cl A white solid; [α] 25 D = (c 1.0, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.61 (d, J = 7.7 Hz, 1H), (m, 1H), 7.12 (d, J = 8.4 Hz, 2H), 7.00 (t, J = 7.4 Hz, 1H), 6.96 (d, J = 8.3 Hz, 2H), 6.93 (q, J = 2.5 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 4.51 (d, J = 1.5 Hz, 1H), 3.15 (dt, J = 18.9 Hz, 2.0 Hz, 1H), 2.89 (ddd, J = 18.9 Hz, 2.5 Hz, 1.5 Hz, 1H); 13 C NMR (125 MHz, Acetone d 6 ) δ , , , , , , , , , , , , , , , , , , , , , 88.79, 38.93, 31.46, 13.12; HRMS (ESI) m/z calcd for C 23 H 21 ClNa 4 [M + Na] + = , found = ; The ee value was 93%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 1% i PrH/hexane, flow rate = 1.0 ml/min). S5
6 Racemic 5b Enantioenriched 5b tert Butyl (2R,2'S) 2' (3 chlorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5c C 2 tbu Cl A white solid; [α] 25 D = (c 1.0, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 1H), 7.05 (t, J = 7.7 Hz, 2H), 7.00 (t, J = 7.5 Hz, 1H), 6.95 (q, J = 2.5 Hz, 1H), 6.88 (d, J = 7.6 Hz, 1H), 6.74 (dd, J = 8.5 Hz, 0.5 Hz, 1H), 4.50 (d, J = 1.7 Hz, 1H), 3.16 (dt, J = 18.9 Hz, 2.0 Hz, 1H), (m, 1H), 1.25 S6
7 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 95.12, 81.05, 59.22, 41.98, 27.74; HRMS (ESI) m/z calcd for C 23 H 21 ClNa 4 [M + Na] + = , found = ; The ee value was 91%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5c Enantioenriched 5c S7
8 tert Butyl (2R,2'S) 2' (2 chlorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5d Cl C 2 tbu Yellow oil; [α] 25 D = (c 1.0, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.67 (dd, J = 7.7, 0.7 Hz, 1H), 7.46 (ddd, J = 8.5 Hz, 7.3 Hz, 1.4 Hz, 1H), 7.25 (dd, J = 7.7 Hz, 1.6 Hz, 1H), (m, 1H), 7.14 (dd, J = 7.9 Hz, 1.3 Hz, 1H), (m, 1H), (m, 1H), 6.99 (q, J = 2.5 Hz, 1H), 6.70 (d, J = 8.4 Hz, 1H), 5.15 (d, J = 2.2 Hz, 1H), (m, 1H), (m, 1H), 1.22 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 94.08, 80.87, 55.21, 42.30, 27.67; HRMS (ESI) m/z calcd for C 23 H 21 ClNa 4 [M + Na] + = , found = ; The ee value was 91%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5d S8
9 Enantioenriched 5d tert Butyl (2R,2'S) 2' (4 fluorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5e C 2 tbu F A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.60 (dd, J = 7.7, 0.6 Hz, 1H), 7.45 (dd, J = 11.5, 4.0 Hz, 1H), (m, 3H), 6.92 (q, J = 2.4 Hz, 1H), 6.83 (t, J = 8.6 Hz, 2H), 6.71 (d, J = 8.5 Hz, 1H), 4.53 (d, J = 1.7 Hz, 1H), 3.15 (dt, J = 18.9, 1.9 Hz, 1H), 2.89 (dd, J = 18.9, 1.7 Hz, 1H), 1.24 (s, 11H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , (d, J = Hz), , , , (d, J = 3.2 Hz), (d, J = 8.1 Hz), , , , , (d, J = 21.3 Hz), , 95.30, 80.89, 59.10, 41.80, 27.76; HRMS (ESI) m/z calcd for C 23 H 21 FNa 4 [M + Na] + = , found = ; The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). S9
10 Racemic 5e Enantioenriched 5e tert Butyl (2R,2'S) 2' (4 methoxyphenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5f C 2 tbu Me A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), 7.44 (t, J = 7.8 Hz, 1H), 6.98 (t, J = 7.5 Hz, 1H), 6.93 (d, J = 8.4 Hz, 2H), 6.90 (q, J = 2.2 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.68 (d, J = 8.4 Hz, 2H), 4.50 (d, J = 1.4 Hz, 1H), 3.72 (s, 3H), 3.14 (d, J = 18.9 Hz, 1H), 2.88 (d, J = 18.9 Hz, 1H), 1.25 (s, 10H); 13 C NMR S10
11 (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 95.54, 80.71, 59.10, 55.12, 41.78, 27.78; HRMS (ESI) m/z calcd for C 24 H 24 Na 5 [M + Na] + = , found = ; The ee value was 96%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5f Enantioenriched 5f S11
12 tert Butyl (2R,2'S) 3 oxo 2' (p tolyl) 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5g C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), 7.44 (ddd, J = 8.5 Hz, 7.3 Hz, 1.4 Hz, 1H), 6.98 (t, J = 7.4 Hz, 1H), 6.94 (d, J = 8.0 Hz, 2H), (m, 3H), 6.73 (d, J = 8.4 Hz, 1H), 4.51 (d, J = 2.0 Hz, 1H), 3.14 (dt, J = 18.9, 2.0 Hz, 1H), 2.89 (ddd, J = 18.8, 2.6, 1.6 Hz, 1H), 2.23 (s, 3H), 1.25 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 95.46, 80.70, 59.29, 41.89, 27.75, 21.07; HRMS (APCI) m/z calcd for C 24 H 24 Na 4 [M + Na] + = , found = ; The ee value was 95%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5g S12
13 Enantioenriched 5g tert Butyl (2R,2'S) 3 oxo 2' (o tolyl) 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5h C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.62 (d, J = 7.7 Hz, 1H), (m, 1H), (m, 1H), 7.10 (t, J = 7.4 Hz, 1H), (m, 2H), 6.91 (dt, J = 5.8 Hz, 2.8 Hz, 2H), 6.72 (d, J = 8.4 Hz, 1H), 4.84 (d, J = 2.1 Hz, 1H), (m, 1H), (m, 1H), 2.02 (s, 3H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 95.02, 80.61, 54.85, 42.19, 27.62, 19.49; HRMS (ESI) m/z calcd for C 24 H 24 Na 4 [M + Na] + = , found = ; The ee value was 97%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). S13
14 Racemic 5h Enantioenriched 5h tert Butyl (2R,2'S) 2' (4 cyanophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5i C 2 tbu NC A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.62 (d, J = 7.6 Hz, 1H), (m, 3H), 7.15 (d, J = 8.1 Hz, 2H), (m, 2H), 6.69 (d, J = 8.4 Hz, 1H), 4.59 (s, 1H), 3.19 (dt, J = 19.0 Hz, 1.9 Hz, 1H), (m, 1H), 1.25 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , S14
15 137.23, , , , , , , , , 94.96, 81.30, 59.52, 42.12, 27.77; HRMS (ESI) m/z calcd for C 24 H 21 NNa 4 [M + Na] + = , found = ; The ee value was 93%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5i Enantioenriched 5i tert Butyl (2R,2'S) 2' (naphthalen 2 yl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5j C 2 tbu S15
16 A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), 7.66 (m, 2H), 7.61 (dd, J = 7.8 Hz, 0.6 Hz, 1H), 7.47 (s, 1H), (m, 2H), (m, 1H), 7.21 (dd, J = 8.4 Hz, 1.1 Hz, 1H), 6.99 (q, J = 2.5 Hz, 1H), 6.92 (t, J = 7.5 Hz, 1H), 6.62 (d, J = 8.5 Hz, 1H), 4.74 (d, J = 1.7 Hz, 1H), 3.20 (dt, J = 18.8, 1.9 Hz, 1H), (m, 1H), 1.15 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , 95.65, 80.81, 59.65, 42.21, 27.69; HRMS (ESI) m/z calcd for C 27 H 24 Na 4 [M + Na] + = , found = ; The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5j S16
17 Enantioenriched 5j tert Butyl (2R,2'S) 2' (3,4 dimethoxyphenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5k C 2 tbu Me Me A white solid; [α] 25 D = 99.8 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.60 (d, J = 7.6 Hz, 1H), (m, 1H), 6.98 (t, J = 7.5 Hz, 1H), (m, 1H), 6.71 (d, J = 8.4 Hz, 1H), 6.62 (d, J = 8.2 Hz, 1H), 6.54 (dd, J = 8.2 Hz, 1.6 Hz, 1H), 6.51 (s, 1H), 4.50 (s, 1H), 3.78 (s, 3H), 3.71 (s, 3H), 3.14 (d, J = 18.9 Hz, 1H), (m, 1H), 1.26 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 95.62, 80.79, 59.55, 55.79, 55.72, 41.75, 27.81; HRMS (ESI) m/z calcd for C 25 H 26 Na 6 [M + Na] + = , found = ; The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 20% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5k S17
18 Enantioenriched 5k tert Butyl (2R,2'S) 3 oxo 2' (thiophen 2 yl) 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5l C 2 tbu S A yellow solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), 7.11 (d, J = 5.1 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), (m, 1H), 6.87 (d, J = 8.5 Hz, 1H), 6.80 (dd, J = 5.0 Hz, 3.6 Hz, 1H), 6.72 (d, J = 3.4 Hz, 1H), 4.84 (d, J = 1.7 Hz, 1H), 3.13 (dt, J = 18.8 Hz, 1.9 Hz, 1H), (m, 1H), 1.29 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , 94.85, 80.96, 54.29, 41.39, 27.78; HRMS (ESI) m/z calcd for C 21 H 20 Na 4 S [M + Na] + = , found = ; The ee value was 95%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). S18
19 Racemic 5l Enantioenriched 5l tert Butyl (2R,2'S) 2' cyclohexyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5m C 2 tbu Colorless oil; [α] 25 D = 52.3 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (d, J = 7.7 Hz, 1H), (m, 1H), 7.11 (dd, J = 7.9 Hz, 5.1 Hz, 2H), 6.67 (q, J = 2.4 Hz, 1H), 3.33 (d, J = 1.6 Hz, 1H), 2.83 (dd, J = 18.6 Hz, 1.4 Hz, 1H), (m, 1H), (m, 1H), (m, 6H), 1.53 (s, 9H), (m, 2H), (m, 1H), 0.88 (qd, J = 12.4 Hz, 3.3 Hz, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , S19
20 122.02, , , 96.41, 80.78, 56.05, 43.00, 38.62, 30.47, 30.41, 28.14, 27.20, 27.09, 26.53; HRMS (ESI) m/z calcd for C 23 H 28 Na 4 [M + Na] + = , found = ; The ee value was 95%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 1% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5m Enantioenriched 5m tert Butyl (2R,2'S) 2' isopropyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5n C 2tBu S20
21 A white solid; [α] 25 D = 31.7 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.71 (dd, J = 7.9 Hz, 1.1 Hz, 1H), (m, 1H), 7.11 (dd, J = 8.2 Hz, 6.2 Hz, 2H), 6.70 (q, J = 2.4 Hz, 1H), 3.37 (dd, J = 3.5 Hz, 1.8 Hz, 1H), (m, 1H), (m, 1H), 2.36 (dtd, J = 14.2 Hz, 7.1 Hz, 4.0 Hz, 1H), 1.52 (s, 9H), 1.05 (d, J = 7.1 Hz, 3H), 0.81 (d, J = 7.1 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , 96.55, 80.76, 56.47, 43.05, 28.13, 27.99, 19.96, 19.64; HRMS (ESI) m/z calcd for C 20 H 24 Na 4 [M + Na] + = , found = ; The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5n Enantioenriched 5n S21
22 tert Butyl (2R,2'S) 2' butyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5o C 2 tbu Colorless oil; [α] 25 D = 21 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (dd, J = 7.9 Hz, 1.1 Hz, 1H), 7.64 (ddd, J = 8.5 Hz, 7.3 Hz, 1.4 Hz, 1H), (m, 2H), 6.66 (q, J = 2.5 Hz, 1H), (m, 1H), 2.94 (ddd, J = 18.9 Hz, 2.3 Hz, 1.6 Hz, 1H), (m, 1H), (m, 1H), 1.71 (ddd, J = 18.6 Hz, 9.5Hz, 4.7 Hz, 1H), 1.52 (s, 9H), (m, 4H), (m, 1H), 0.74 (t, J = 7.2 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 95.82, 80.76, 52.31, 43.18, 29.76, 28.16, 26.55, 22.68, 13.74; HRMS (ESI) m/z calcd for C 21 H 26 Na 4 [M + Na] + = , found = ; The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 0.5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 5o S22
23 Enantioenriched 5o tert Butyl (2R,2'S) 2' ethyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 3' ene 3' carboxylate 5p C 2 tbu Colorless oil; [α] 25 D = 4.8 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.71 (d, J = 7.6 Hz, 1H), 7.65 (dd, J = 12.0 Hz, 4.7 Hz, 1H), 7.12 (dd, J = 11.9 Hz, 5.2 Hz, 2H), 6.68 (q, J = 2.3 Hz, 1H), (m, 1H), 2.94 (dd, J = 18.9 Hz, 1.5 Hz, 1H), 2.76 (dd, J = 18.9 Hz, 1.8 Hz, 1H), 1.86 (dqd, J = 15.0 Hz, 7.5 Hz, 3.2 Hz, 1H), (m, 1H), 1.66 (t, J = 5.0 Hz, 1H), 0.71 (t, J = 7.4 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 95.82, 80.77, 53.63, 43.21, 28.15, 20.13, 12.14; HRMS (ESI) m/z calcd for C 19 H 22 Na 4 [M + Na] + = , found = ; The ee value was 96%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 1% i PrH/hexane, flow rate = 1.0 ml/min). S23
24 Racemic 5p Enantioenriched 5p tert Butyl (2R,5'S) 3 oxo 5' phenyl 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6a C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.57 (dd, J = 7.7 Hz, 0.8 Hz, 1H), 7.44 (t, J = 2.4 Hz, 1H), 7.40 (ddd, J = 8.5 Hz, 7.3 HZ, 1.4 Hz, 1H), (m, 5H), 6.92 (t, J = 7.5 Hz, 1H), 6.78 (d, J = 8.3 Hz, 1H), 3.99 (t, J = 8.0 Hz, 1H), 3.08 (qdd, J = 18.8 Hz, 8.1 Hz, 2.5 Hz, 2H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , S24
25 96.87, 81.58, 54.23, 37.96, 27.61; HRMS (ESI) m/z calcd for C 23 H 22 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6a Enantioenriched 5q tert Butyl (2R,5'S) 5' (4 chlorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6b C 2 tbu Cl S25
26 A white solid; [α] 25 D = (c 0.5, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.58 (d, J = 7.6 Hz, 1H), (m, 1H), 7.42 (t, J = 2.4 Hz, 1H), (m, 4H), 6.96 (t, J = 7.4 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 3.95 (t, J = 8.1 Hz, 1H), (m, 2H), 1.16 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 96.59, 81.72, 53.48, 38.16, 27.60; HRMS (ESI) m/z calcd for C 23 H 21 ClNa 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6b Enantioenriched 6b S26
27 tert Butyl (2R,5'S) 5' (3 chlorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6c C 2 tbu Cl A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.60 (d, J = 7.6 Hz, 1H), (m, 1H), 7.42 (t, J = 2.4 Hz, 1H), 7.24 (s, 1H), (m, 3H), 6.96 (t, J = 7.5 Hz, 1H), 6.84 (d, J = 8.3 Hz, 1H), 3.95 (t, J = 8.0 Hz, 1H), (m, 2H), 1.18 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 96.54, 81.72, 53.66, 38.06, 27.61; HRMS (ESI) m/z calcd for C 27 H 24 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6c S27
28 Enantioenriched 6c tert Butyl (2R,5'S) 3 oxo 5' (o tolyl) 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6d C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.58 (d, J = 7.6 Hz, 1H), 7.45 (t, J = 2.4 Hz, 1H), (m, 2H), 7.13 (t, J = 7.4 Hz, 1H), 7.01 (t, J = 7.4 Hz, 1H), 6.93 (t, J = 7.4 Hz, 2H), 6.81 (d, J = 8.4 Hz, 1H), 4.35 (t, J = 7.8 Hz, 1H), 3.06 (dddd, J = 19.1 Hz, 9.9 Hz, 7.8 Hz, 2.5 Hz, 2H), 2.16 (s, 3H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 96.72, 81.55, 48.56, 39.54, 27.61, 19.88; HRMS (ESI) m/z calcd for C 24 H 24 Na 4 [M + Na] + = , found = ; The ee value was 99%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). S28
29 Racemic 6d Enantioenriched 6d tert Butyl (2R,5'S) 5' (4 bromophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6e C 2tBu Br A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.58 (d, J = 7.6 Hz, 1H), (m, 1H), 7.41 (t, J = 2.4 Hz, 1H), 7.29 (d, J = 8.3 Hz, 3H), 7.07 (d, J = 8.4 Hz, 2H), 6.96 (t, J = 7.4 Hz, 1H), 6.82 (d, J = 8.2 Hz, 1H), 3.94 (t, J = 8.0 Hz, 1H), (m, 2H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , S29
30 151.31, , , , , , , , , , , 96.53, 81.72, 53.51, 38.14, 27.60; HRMS (ESI) m/z calcd for C 23 H 21 BrNa 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 20% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6e Enantioenriched 6e S30
31 tert Butyl (2R,5'S) 5' (4 methoxyphenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6f C 2 tbu Me A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.56 (dd, J = 7.7 Hz, 0.8 Hz, 1H), 7.41 (ddd, J = 9.9 Hz, 6.0 Hz, 1.4 Hz, 2H), (m, 2H), 6.92 (dd, J = 11.4 Hz, 4.1 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), (m, 2H), 3.94 (t, J = 8.1 Hz, 1H), 3.69 (s, 3H), 3.02 (dd, J = 8.1 Hz, 2.5 Hz, 2H), 1.16 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 96.90, 81.56, 55.10, 53.63, 38.33, 27.60; HRMS (ESI) m/z calcd for C 24 H 24 Na 5 [M + Na] + = , found = ; The ee value was 99%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6f S31
32 Enantioenriched 6f tert Butyl (2R,5'S) 3 oxo 5' (p tolyl) 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6g C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), 7.07 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.93 (t, J = 7.5 Hz, 1H), 6.81 (d, J = 8.2 Hz, 1H), 3.96 (t, J = 8.0 Hz, 1H), (m, 2H), 2.21 (s, 3H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 96.91, 81.53, 53.90, 38.20, 27.61, 20.99; HRMS (ESI) m/z calcd for C 24 H 24 Na 4 [M + Na] + = , found = ; The ee value was 99%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). S32
33 Racemic 6g Enantioenriched 6g tert Butyl (2R,5'S) 3 oxo 5' (m tolyl) 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6h C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.58 (d, J = 7.4 Hz, 1H), 7.42 (dd, J = 8.3 Hz, 7.3 Hz, 2H), 7.04 (t, J = 7.7 Hz, 1H), 6.99 (d, J = 2.9 Hz, 2H), 6.93 (t, J = 7.2 Hz, 2H), 6.79 (d, J = 8.3 Hz, 1H), 3.95 (t, J = 8.0 Hz, 1H), (m, 2H), 2.22 (s, 3H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , S33
34 151.73, , , , , , , , , , , , , 96.91, 81.56, 54.17, 38.02, 27.62, 21.23; HRMS (ESI) m/z calcd for C 24 H 24 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6h Enantioenriched 6h S34
35 tert Butyl (2R,5'S) 5' (4 fluorophenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6i C 2 tbu F A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.57 (dd, J = 7.7 Hz, 0.9 Hz, 1H), 7.43 (ddd, J = 9.0 Hz, 6.0 Hz, 1.9 Hz, 2H), (m, 2H), (m, 1H), (m, 3H), 3.96 (t, J = 8.1 Hz, 1H), (m, 2H), 1.17 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , (d, J = Hz), , , , , (d, J = 3.2 Hz), (d, J = 8.0 Hz), , , , (d, J = 21.3 Hz), , 96.67, 81.66, 78.41, 53.48, 38.23, 27.61; HRMS (ESI) m/z calcd for C 23 H 21 FNa 4 [M + Na] + = , found = ; The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 20% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6i S35
36 Enantioenriched 6i tert Butyl (2R,5'S) 5' (naphthalen 2 yl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6j C 2 tbu A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.72 (dd, J = 9.0 Hz, 4.8 Hz, 2H), (m, 2H), (m, 1H), 7.48 (t, J = 2.4 Hz, 1H), 7.39 (ddd, J = 10.1 Hz, 8.1 Hz, 3.1 Hz, 3H), (m, 1H), 6.87 (t, J = 7.4 Hz, 1H), 6.75 (d, J = 8.3 Hz, 1H), 4.18 (t, J = 8.0 Hz, 1H), 3.17 (dddd, J = 21.7 Hz, 18.8 Hz, 8.0 Hz, 2.5 Hz, 2H), 1.18 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , 97.09, 81.64, 54.27, 38.38, 27.62; HRMS (ESI) m/z calcd for C 27 H 24 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). S36
37 Racemic 6j Enantioenriched 6j tert Butyl (2R,5'S) 5' (3,4 dimethoxyphenyl) 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6k C 2 tbu Me Me A white solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.57 (d, J = 7.8 Hz, 1H), 7.42 (ddd, J = 6.0 Hz, 4.9 Hz, 1.4 Hz, 2H), 6.94 (t, J = 7.4 Hz, 1H), 6.80 (d, J = 8.3 Hz, 1H), 6.73 (dd, J = 8.2 Hz, 1.8 Hz, 1H), 6.68 (d, J = S37
38 1.7 Hz, 1H), 6.65 (d, J = 8.3 Hz, 1H), 3.94 (t, J = 8.1 Hz, 1H), 3.77 (s, 3H), 3.73 (s, 3H), (m, 2H), 1.16 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 96.96, 81.62, 55.81, 55.71, 53.94, 38.08, 27.60; HRMS (ESI) m/z calcd for C 25 H 26 Na 6 [M + Na] + = , found = ; The ee value was 99%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 20% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6k Enantioenriched 6k S38
39 tert Butyl (2R,5'R) 3 oxo 5' (thiophen 2 yl) 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6l C 2 tbu S A yellow solid; [α] 25 D = (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), 7.39 (t, J = 2.4 Hz, 1H), (m, 1H), 6.99 (t, J = 7.4 Hz, 1H), 6.92 (d, J = 8.4 Hz, 1H), 6.78 (d, J = 3.4 Hz, 2H), 4.31 (t, J = 8.1 Hz, 1H), 3.09 (dddd, J = 20.6 Hz, 18.6 Hz, 8.1Hz, 2.5 Hz, 2H), 1.18 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , 96.17, 81.72, 49.25, 39.92, 27.62; HRMS (ESI) m/z calcd for C 21 H 20 Na 4 S [M + Na] + = , found = ; The ee value was 99%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 10% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6l S39
40 Enantioenriched 6l tert Butyl (2R,5'S) 5' cyclohexyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6m C 2 tbu Colorless oil; [α] 25 D = 32.1 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (dd, J = 7.8 Hz, 1.2 Hz, 1H), 7.60 (ddd, J = 8.6 Hz, 7.3 Hz, 1.4 Hz, 1H), (m, 1H), (m, 2H), 2.72 (ddd, J = 17.8 Hz, 7.0 Hz, 3.0 Hz, 1H), (m, 1H), 2.54 (ddd, J = 17.8 Hz, 7.9 Hz, 2.1 Hz, 1H), 1.77 (d, J = 12.8 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 1.12 (s, 9H), (m, 4H), (m, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 97.30, 81.39, 54.29, 37.18, 35.39, 32.48, 31.29, 27.59, 26.14, 26.11, 25.79; HRMS (ESI) m/z calcd for C 23 H 28 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 3% i PrH/hexane, flow rate = 1.0 ml/min). S40
41 Racemic 6m Enantioenriched 6m tert Butyl (2R,5'S) 5' isopropyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6n C 2 tbu A while solid; [α] 25 D = 47.4 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (dd, J = 7.9, 1.1 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), 1.12 (s, 9H), 0.94 (d, J = 6.7 Hz, 3H), 0.60 (d, J = 6.6 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 97.40, 81.40, 55.52, 35.76, 27.85, 27.58, 22.19, 21.17; HRMS S41
42 (ESI) m/z calcd for C 20 H 24 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6n Enantioenriched 6n tert Butyl (2R,5'R) 5' butyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6o C 2 tbu S42
43 Colorless oil; [α] 25 D = (c 0.5, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (d, J = 7.6 Hz, 1H), (m, 1H), 7.29 (t, J = 2.4 Hz, 1H), (m, 2H), 2.83 (ddd, J = 18.4 Hz, 7.5 Hz, 3.0 Hz, 1H), 2.73 (dtd, J = 9.8 Hz, 7.5 Hz, 5.1 Hz, 1H), 2.42 (ddd, J = 18.4 Hz, 7.5, 2.0 Hz, 1H), (m, 2H), (m, 3H), 1.15 (s, 9H), (m, 1H), 0.79 (t, J = 7.1 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 97.73, 81.38, 48.48, 37.63, 30.05, 27.88, 27.59, 22.63, 13.86; HRMS (ESI) m/z calcd for C 21 H 26 Na 4 [M + Na] + = , found = ; The ee value was 97%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6o Enantioenriched 6o S43
44 tert Butyl (2R,5'R) 5' ethyl 3 oxo 3H spiro[benzofuran 2,1' cyclopentan] 2' ene 2' carboxylate 6p C 2 tbu Colorless oil; [α] 25 D = 98.2 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), 7.30 (t, J = 2.4 Hz, 1H), (m, 2H), 2.85 (ddd, J = 18.5 Hz, 7.5 Hz, 3.0 Hz, 1H), (m, 1H), 2.42 (ddd, J = 18.6 Hz, 7.6 Hz, 2.0 Hz, 1H), (m, 1H), (m, 1H), 1.15 (s, 9H), 0.80 (t, J = 7.4 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , , , 97.65, 81.39, 50.21, 37.33, 27.59, 21.43, 12.35; HRMS (ESI) m/z calcd for C 19 H 22 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 6p S44
45 Enantioenriched 6p E. Synthesis of product 8 C 2 tbu H 2 C 2 tbu 30% TFA CH Pd/C DCM 6n (98% ee) 7 8 dr > 19:1 90% yield 97 % ee dr > 19:1 94% yield 98 % ee To 6n (65.7 mg, 0.2 mmol) in methanol (2 ml) was added Pd/C (6.6 mg, 10%), and H 2 was introduced to the system. After 12 hour, Pd/C was removed by filtration. The mixture was concentrated, and the residue was purified by flash column chromatography (hexane/ether = 10 : 1) to afford 7 as a colorless oil (59.5 mg, >19:1 dr, 90% yield). 7: [α] 25 D = 50.8 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ 7.70 (d, J = 7.5 Hz, 1H), (m, 1H), 7.09 (t, J = 7.8 Hz, 2H), 3.38 (dd, J = 10.3 Hz, 8.2 Hz, 1H), (m, 1H), 2.21 (dt, J = 11.9 Hz, 8.0 Hz, 1H), (m, 2H), 1.86 (ddd, J = 18.4 Hz, 11.6 Hz, 7.2 Hz, 1H), 1.61 (dq, J = 13.5, 6.7 Hz, 1H), 0.97 (s, 9H), 0.84 (d, J = 6.7 Hz, 3H), 0.58 (d, J = 6.7 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , , 97.90, 81.01, 57.14, 54.79, 28.33, 27.60, 27.39, 23.83, 23.00, 21.31; HRMS (ESI) m/z calcd for C 20 H 26 Na 4 S45
46 [M + Na] + = , found = ; The ee value was 97%, t R (minor) = min, t R (major) = min (Chiralpak IC, λ = 254 nm, 5% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 7 Enantioenriched 7 To a CH 2 Cl 2 (1.5 ml) solution of 7 (59.5 mg, 0.18 mmol) at 0 o C was added trifluoroacetic acid (0.75 ml, 30%) dropwise. The mixture was stirred at room temperature for 2 h, and the solvent was removed. The crude product was then purified by flash column chromatography (hexane/ethyl acetate = 1 : 2) to afford 8 as a colorless oil (46.4 mg, >19:1 dr, 94% yield). S46
47 8: [α] 25 D = 54.2 (c 1, CHCl 3 ); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 2H), 3.41 (t, J = 9.0 Hz, 1H), (m, 1H), 2.16 (dt, J = 11.7 Hz, 8.0 Hz, 1H), (m, 2H), (m, 1H), 1.58 (tt, J = 13.5 Hz, 6.7 Hz, 1H), 0.82 (d, J = 6.7 Hz, 3H), 0.54 (d, J = 6.7 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ , , , , , , , 97.16, 56.83, 53.80, 28.40, 27.58, 24.23, 22.87, 21.30; HRMS (ESI) m/z calcd for C 16 H 18 Na 4 [M + Na] + = , found = ; The ee value was 98%, t R (major) = min, t R (minor) = min (Chiralpak IC, λ = 254 nm, 30% i PrH/hexane, flow rate = 1.0 ml/min). Racemic 8 Enantioenriched 8 S47
48 F. Determination of stereochemistry of product 8 by 2D NMR H a H b Figure S1. CSY spectrum for product 8 S48
49 H a H b Figure S2. NSEY spectrum of product 8 Proton H a and H b were identified using CSY. NSEY showed the two protons had correlations, which suggested they were on the same side of the cyclopentane ring. Therefore, the stereochemistry of the newly installed chiral center in product 8 could be determined as shown in the structure. G. Computational methods Density functional theory (DFT) methods, as implemented in the Gaussian 09 program 3, have been employed to study the phosphine catalyzed [3+2] annulation. Molecular geometries of the complexes were optimized via DFT calculations using the B3LYP 4 /6 31G(d) 5 level of theory. The vibrational frequencies were computed at the same S49
50 level of theory to determine whether the optimized structure was at an energy minimun. Solvent effects were determined within SMD 6 model (toluene) at the M11 7 /6 311+G(d) 8 level of theory using gas phase optimized geometries. H. Proposed Reaction Cycle and DFT studies The plausible mechanism for the phosphine catalyzed [3+2] annulation of aurone with allene is shown in Scheme S1. Based on the previous exploration of phosphine catalyzed [3+2] annulation reactions, we proposed that the reaction is initially undergoes the nucleophilic attack of the phosphine catalyst A on allene 2a to give a zwitterionic species B. The allenoate moiety of intermediate B exists two resonance structures (C or G), in which the negative charge could be attributed to the α or γ position, respectively. The followed nucleophilic addition could take place with either α or γ position with aurone 1 to yield zwitterionic intermediate D or H, respectively. Subsequently, the stepwise [3+2] annulation yields phosphorus ylide E or I. Then the proton transfer affords α annulation product 5 or γ annulation product 6, respectively, and regenerates the active catalyst A. C 2 tbu E PR 3 C 2 tbu F PR 3 R C 2 tbu 5 R 6 R C 2 tbu -annulation pathway PR 3 A C 2 tbu 2a tbu 2 C R R R PR 3 C 2 tbu PR 3 C 2 tbu B 1 1 PR3 PR 3 R C 2 tbu tbu 2 C D C G R J -annulation pathway PR 3 tbu 2 C tbu 2 C R H I R PR 3 PR 3 Scheme S1. Proposed mechanism for the phosphine catalyzed [3+2] annulation of aurones with allenes. S50
51 Figure S3. The B3LYP calculated NPA charge distributions for intermediate 12 int and 25 int. Figure S4. ptimized transition states 14 ts re (indicated as TS 1 in the main article), 18 ts si (TS 2), 27 ts re (TS 3) and 31 ts si (TS 4). The relative free energies are given in kilocalories per mole. S51
52 I. Calculated Gibbs free energy profiles for the phosphine catalyzed [3+2] annulation of aurone 1a and allene 2a. Figure S5. The DFT computed energy surfaces of the catalyst 4e catalyzed [3+2] annulation of aurone 1a and allene 2a. S52
53 G (kcal/mol) H (kcal/mol)) TBDPS Ph P Ph N H H ipr N H tbu F 3 C tbu 2a 0.0 (0.0) 4c 23-ts CF (-9.1) 22-int TBDPS Ph P Ph N H ipr H N H tbu CF 3 F 3 C 22-int 16.3 (1.3) 23-ts 2.4 (-13.4) 24-int nucleophilic attack 1a 6.0 (-8.6) 25-int TBDPS Ph P Ph tbu N H ipr H N H CF 3 F 3 C 27-ts-re 5.1 (-26.0) 26-int 9.4 (-23.8) 27-ts-re TBDPS TBDPS TBDPS TBDPS Ph Ph Ph Ph P Ph P Ph P Ph P Ph N N tbu N tbu H N H H H ipr H ipr H ipr H N H N H ipr H tbu NH N H CF 3 CF 3 CF 3 CF 3 F 3 C F 3 C F 3 C F 3 C 4c 24-int 25-int 26-int TBDPS Ph tbu P Ph N H H CF ipr N 3 H CF 3 31-ts-si TBDPS Ph P Ph tbu N H ipr H N H F 3 C (-45.2) 28-int-re CF 3 28-int-re 5.1 (-28.1) 29-ts-re C 2 tbu Ph 6-re -2.6 (-34.5) 30-int-re TBDPS Ph tbu P Ph N H H ipr N CF 3 H CF 3 32-int-si TBDPS F 3 C 16.3 (-14.6) 31-ts-re 7.5 (-25.0) 31-ts-si C 2 tbu Ph 6-si tbu N H ipr H NH CF 3 Ph P Ph 29-ts-re -7.1 (-39.8) 32-int-re (-45.6) 32-int-si 5-re (49.6) 4c 3.2 (-29.7) 33-ts-si TBDPS Ph P Ph tbu N H H ipr CF 3 N H 33-ts-si 6.7 (-26.5) 33-ts-re CF 3 TBDPS F 3 C tbu N H ipr H NH CF (-38.1) 34-int-si Ph P Ph 30-int-re -6.7 (-37.3) 34-int-re C 2 tbu Ph 5-re TBDPS Ph P Ph tbu N H H ipr CF 3 N H 34-int-si (50.8) 4c (50.8) 4c TBDPS TBDPS TBDPS TBDPS Ph Ph Ph Ph P Ph P Ph P Ph N N N tbu P Ph N tbu H tbu H tbu H H ipr H ipr H ipr H H ipr N H N H N H N H CF 3 CF 3 CF 3 CF 3 F 3 C F 3 C F 3 C F 3 C 31-ts-re 32-int-re 33-ts-re 34-int-re annulation (si-face attack) annulation (re-face attack) annulation (re-face attack) 6-re 6-si CF 3 Figure S6. The DFT computed energy surfaces of the catalyst 4c catalyzed [3+2] annulation of aurone 1a and allene 2a. S53
54 Figure S7. ptimized transition states 14 ts re, 14 ts si, 31 ts re and 31 ts si. The relative free energies are given in kilocalories per mole. S54
55 J. B3LYP and M11 absolute calculation energies, enthalpies, and free energies. Geometry E B3LYP(elec) 1 E M11(toluene) 2 Correction of Correction of IF H (gas phase) G (gas phase) 4e c a a re si re si int ts int int int ts re(ts 1) int re ts re int re ts si int si ts si int si ts si(ts 2) int si ts si int si int ts S55
56 24 int int int ts re(ts 3) int re ts re int re ts re int re ts re int re ts si(ts 4) int si ts si int si The electronic energy calculated by B3LYP in gas phase. 2 The electronic energy calculated by M11 in toluene. 3 The thermal correction to enthalpy calculated by B3LYP in gas phase. 4 The thermal correction to Gibbs free energy calculated by B3LYP in gas phase. 5 The B3LYP calculated imaginary frequencies for the transition states in gas phase. S56
57 K. B3LYP geometries for all the optimized compounds and transition states. 4e P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C H C C S57
58 C C H C H C H C C F F F F F F c P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C C C H H H C H S58
59 H H N H C H C C C C H C H C H C C F F F F F F H a C C H H C H C C C H H H C H H H C H H H a C C C C C C C C H H H H C H C C C C H C H C H H H re C C C C C C C C H H H H C H C C C C S59
60 H C H C H H H C C H H C C C C H H H C H H H C H H H H si C C C C C C C C H H H H C H C C C C H C H C H H H C C H H C C C C H H H C H H H C H H H H re C C C C C C C C H H H H C H C C S60
61 C C H C H C H H H C C H H C C C C H H H C H H H C H H H H si C C C C C C C C H H H H C H C C C C H C H C H H H C C H H C C C C H H H C H H H C H H H H int P C H H C H C H C H H H C C C C S61
62 H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C S62
63 C H C H C H C C F F F F F F ts P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H S63
64 H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F int P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H S64
65 C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F int P C H H C H C H C H H H C C C C H C H C S65
66 H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H S66
67 C H C C F F F F F F int P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H S67
68 C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C S68
69 H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F S69
70 F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H S70
71 H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H S71
72 H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H S72
73 H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H S73
74 C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C S74
75 H C H H H ts-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H S75
76 H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H S76
77 Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C S77
78 C C C C H H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C S78
79 C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-si P C H H C H C H C H H H C C C C S79
80 H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C S80
81 C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H S81
82 H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H S82
83 19-int-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C S83
84 C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C S84
85 C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H S85
86 H H H C H C C C C H C H C H H H int-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H S86
87 H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int P C H H C H C H C H H H C C C C H C H C H S87
88 H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C S88
89 H C C F F F F F F ts P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C S89
90 C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F int P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H S90
91 H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F int P C H H C H C H C H H H C C C C H C H C H H H C C S91
92 C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F S92
93 F F F F F int P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H S93
94 H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H S94
95 Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C S95
96 C C C C H H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C S96
97 C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-re P C H H C H C H C H H H C C C C S97
98 H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C S98
99 C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H S99
100 H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H S100
101 31-ts-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C S101
102 C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C S102
103 C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H S103
104 H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H S104
105 H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-si P C H H C H C H C H H H C C C C H C H C H S105
106 H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C S106
107 H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H S107
108 H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H ts-si P C H S108
109 H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H S109
110 H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H int-re P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C S110
111 H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H S111
112 C H C C C C H C H C H H H int-si P C H H C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H Si C C C C H C H C H H H C C C C H C H C H H H C C H H H C H H H C H H H N H C C H C C H H H C H H S112
113 H N H C C C H H C H C C H C H H H C H H H C H H H C C C C H C H C H C C F F F F F F C C C C C C C C H H H H C H C C C C H C H C H H H S113
114 L. References [1] a) X. Han, Y. Wang, F. Zhong, Y. Lu, J. Am. Chem. Soc. 2011, 133, b) X. Han, F. Zhong, Y. Wang, Y. Lu, Angew. Chem. Int. Ed. 2012, 51, 767 c) F. Zhong, X. Han, Y. Wang, Y. Lu, Chem. Sci. 2012, 3, 1231 d) F. Zhong, X. Han, Y. Wang, Y. Lu, Angew. Chem. Int. Ed. 2011, 50, 7837 e) F. Zhong, J. Luo, G. Y. Chen, X. Dou, Y. Lu, J. Am. Chem. Soc. 2012, 134, f) F. Zhong, X. Dou, X. Han, W. Yao, Q. Zhu, Y. Meng, Y. Lu, Angew. Chem. Int. Ed. 2013, 52, 943 g) W. Yao, X. Dou, Y. Lu, J. Am. Chem. Soc. 2015, 137, 54. [2] H. M. Sim, K. Y. Loh, W. K. Yeo, C. Y. Lee, M. L. Go ChemMedChem 2011, 6, 713. [3] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,. Kitao, H. Nakai, T. Vreven, J. J. A. Montgomery, J. E. Peralta, F. gliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,. Farkas, J. B. Foresman, J. V. rtiz, J. Cioslowski, D. J. Fox, Gaussian 09, revision D.01, Gaussian, Inc.: Wallingford, CT, [4] (a) A. D. Becke, J. Chem. Phys. 1993, 98, (b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785. (c) P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, S114
115 [5] (a) W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, (b) J. D. Dill, J. A. Pople, J. Chem. Phys. 1975, 62, (c) M. M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, M. S. Gordon, D. J. DeFrees, J. A. Pople, J. Chem. Phys. 1982, 77, 3654 [6] A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2009, 113, [7] R. Peverati, D. G. Truhlar. J. Phys. Chem. Lett. 2011, 2, [8] (a) R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650. (b) A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, S115
116 M. NMR Spectra of the Products S116
117 f1 (ppm) S117
118 S118
119 Cl 5d C 2 tbu Cl 5d C 2 tbu f1 (ppm) S119
120 f1 (ppm) S120
121 f1 (ppm) S121
122 f1 (ppm) S122
123 f1 (ppm) S123
124 S124
125 S125
126 Me Me C 2 tbu 5k Me Me C 2 tbu 5k S126
127 S127
128 S128
129 C 2 tbu 5n C 2 tbu 5n S129
130 S130
131 S131
132 S132
133 S133
134 S134
135 S135
Supplementary Figure 1. 1 H and 13 C NMR spectra for compound 1a
216.29 185.02 164.20 148.97 128.19 87.70 79.67 77.30 77.04 76.79 74.66 26.23 2.02 2.03 2.01 3.05 7.26 6.92 6.90 6.25 6.23 5.61 5.60 5.58 5.25 5.24 1.58 Supplementary Figure 1. 1 H and 13 C NMR spectra
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