-Supporting information-

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1 -upporting information- Rhodium-Catalyzed [ ] Cycloaddition of ximes with Diynes to Pyridines Fen Xu, Chunxiang Wang, Dongping Wang, Xincheng Li, and Boshun Wan* Dalian Institute of Chemical Physics, Chinese Academy of ciences, 457 Zhongshan Road, Dalian , China. bswan@dicp.ac.cn Table of Contents 1. General information 2 2. General procedure for the [ ] cycloaddition 2 3. Characterization of materials and products References 5 5. Copy of MR ( 1 H, 13 C, 19 F) pectra Copy of HRM pectra

2 1. Experimental 1.1 General All reactions and manipulations were carried out under a dry argon atmosphere either using an inert atmosphere glove-box or standard chlenk techniques. Diynes were prepared according to the published procedure. 1-5 ximes were obtained from the corresponding aldehyde and hydroxylamine 6-8. Unless otherwise noted, commercial reagents were purchased from Aldrich, Alfa Aesar, J&K and used without purification. Anhydrous EtH was distilled over Mg 4 and I 2 before use. Column chromatography was performed on silica gel ( mesh). 1 H, 13 C MR and 19 F MR were recorded on a 500 or 400 MHz Bruker MR spectrometer in CDCl 3 using tetramethylsilane (TM) as the internal standard. HRM data were obtained with Micromass HPLC Q TF mass spectrometer. 2. General procedure for [ ] cycloaddition of diyne 1a-1e and oxime 2a-2n. Rh(CD) 2 BF 4 (5.1 mg, mmol) and dppf (8.3 mg, mmol) were dissolved in CF 3 CH 2 H (6 ml) in the presence of 4Å M, and the mixture was stirred at room temperature for 5 min. xime was added and the resulting mixture was stirred at 80 C for 30 min. To this solution was added diyne (0.25mmol). Then the mixture was stirred at 80 C for 48 h. 4Å M was filtered off and the filtrate was evaporated. The oily residue was purified by column chromatography on silica gel with Petroleum ether/ethyl acetate (polarity from 4:1 to 1:2) to afford 3aa-3an, 3be-3de, 4ea. 3. Characterization of materials and products phenyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3aa. White solid (69% isolated yield), eluent petroleum ether/ethyl acetate = 2:1. 1 H MR (500 MHz, CDCl 3 ) δ 8.52 (d, J = 0.7 Hz, 1H), (m, 2H), (m, 2H), 7.54 (s, 1H), (m, J = 15.8, 7.8, 6.4 Hz, Ts 3H), (m, J = 8.5, 0.5 Hz, 2H), 4.68 (dd, J = 6.2, 1.4 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 157.0, 146.7, 144.1, 144.0, 138.8, 133.6, 131.0, 123.0, 129.2, 128.8, 127.6, 126.9, 114.5, 53.4, 51.7, Ph (4-methoxyphenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ab. White solid (67% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ Ts 8.47 (s, 1H), (m, 2H), (m, J = 8.3 Hz, 2H), 7.47 (s, 1H), (d, J = 8.0 Hz, 2H), (m, 2H), (dd, 4H), 3.85 (s, 3H), 2.40 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 160.7, 156.7, 146.5, 144.0, 143.8, 133.6, 131.4, 130.2, 123.0, 128.2, 127.6, 114.2, 113.7, 55.4, 53.4, 51.7, HRM Calculated forc 21 H [M+H] , found p-tolyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ac. White solid (69% isolated yield) (eluent petroleum ether/ethyl acetate = 4:1 ) 1 H MR (500 MHz, CDCl 3 ) δ 8.50 (s, 1H), 7.80 (dd, J = 13.4, Ts 7.6 Hz, 4H), 7.51 (s, 1H), 7.33 (d, J = 7.6 Hz, 2H), 7.25 (d, J = 6.7 Hz, 2H), 4.67 (d, J = 7.4 Hz, 4H), 2.40 (d, J = 6.7 Hz, 6H). 13 C MR (126 MHz, CDCl 3 ) δ 157.0, 146.6, 144.0, 143.9, 139.3, 136.0, 133.6, 130.7, 123.0, 129.6, 127.6, 126.8, 114.2, 53.4, 51.7, 21.5, HRM Calculated forc 21 H [M+a] , found (4-chlorophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ad. White solid (75% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.51 (s, 1H), (m, 2H), (m, J = 8.3 Hz, 2H), Ts 7.52 (s, 1H), (m, 2H), 7.33 (d, J = 8.0 Hz, 2H), Cl Me

3 (d, J = 4.2 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 155.8, 146.9, 144.1, 144.0, 137.1, 135.5, 133.6, 131.4, 130.0, 129.0, 128.2, 127.6, 114.3, 53.4, 51.7, HRM Calculated for C 20 H 17 Cl 2 2 [M+H] , found (4-fluorophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ae. White solid (88% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.50 (d, J = 0.6 Hz, 1H), 7.90 (m, J = 8.9, 5.4 Hz, 2H), 7.78 (m, J = 8.3 Hz, 2H), 7.50 (s, 1H), 7.33 Ts (dd, J = 8.5, 0.5 Hz, 2H), 7.13 (m, J = 8.7 Hz, 2H), (m, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 164.6, 162.7, 156.0, 146.8, (d, J = 14.9 Hz), 135.0, 133.6, 131.0, 123.0, (d, J F = 8.3 Hz), 127.6, (d, J = 21.7 Hz), 114.2, 53.4, 51.6, F MR (471 MHz, CDCl 3 ) δ (s). HRM Calculated for C 20 H 17 F 2 2 [M+H] , found tosyl-6-(4-(trifluoromethyl)phenyl)-2,3-dihydro-1H-pyrrolo [3,4-c]pyridine 3af. White solid (76% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.55 (s, 1H), 8.04 (d, J = 8.2 Hz, 2H), 7.79 (d, J = 8.2 Hz, Ts 2H), 7.70 (d, J = 8.3 Hz, 2H), 7.59 (s, 1H), 7.34 (d, J = 8.1 Hz, 2H), 4.69 (d, J = 3.4 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 155.4, 146.9, 144.3, 144.1, 142.1, 133.6, 132.0, 131.2, 130.9, 130.0, 127.6, 127.2, (d, J = 3.7 Hz), 114.9, 53.3, 51.7, F MR (471 MHz, CDCl 3 ) δ HRM Calculated for C 21 H 17 F [M+H] , found CF (3-bromophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ag. White solid (78% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ Ts 8.53 (s, 1H), 8.09 (t, J = 1.8 Hz, 1H), 7.83 (m, J = 7.9, 1.6, 1.0 Hz, 1H), (m, 2H), (m, 2H), (m, 3H), 4.68 (dd, J = 8.4, 1.4 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 155.4, 147.0, 144.1, 144.0, 140.7, 133.6, 132.2, 131.7, 130.3, 130.1, 130.0, 127.6, 125.4, 123.1, 114.6, 53.3, 51.6, HRM Calculated for C 20 H 17 Br 2 2 [M+H] , found m-tolyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ah. White solid (81% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.52 (s, 1H), 7.79 (d, J = 8.3 Hz, 2H), 7.75 (s, 1H), 7.68 (d, J = 7.8 Hz, 1H), 7.54 (s, 1H), 7.34 (m, J = 7.8, 5.8 Hz, 3H), 7.22 (d, Ts J = 7.5 Hz, 1H), (m, 4H), 2.41 (s, J = 4.1 Hz, 6H). 13 C MR (126 MHz, CDCl 3 ) δ 157.2, 146.6, 144.1, 143.9, 138.8, 138.5, 133.6, 130.9, 130.0, 128.7, 128.3, 127.7, 127.6, 124.0, 114.6, 53.4, 51.7, 21.5, HRM Calculated for C 21 H [M+H] , found Br tosyl-6-(3-(trifluoromethyl)phenyl)-2,3-dihydro-1Hpyrrolo[3,4-c]pyridine 3ai. White solid (61% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.55 (s, 1H), 8.20 (s, 1H), 8.10 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 7.7 Hz, 1H), (m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.70 (d, J = 3.3 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 155.4, 147.0, 144.2, 144.1, 139.5, 133.6, 131.9, 131.5, 131.2, 130.1, 130.0, 129.3, 127.6, (d, J = 3.7 Hz), (dd, J = 7.4, 3.7 Hz), 114.6, 53.3, 51.7, Ts CF 3 3

4 19 F MR (471 MHz, CDCl 3 ) δ (s) HRM Calculated for C 21 H 17 F [M+H] , found (3-fluorophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3aj. White solid (78% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.52 (s, 1H), 7.79 (d, J = 8.2 Hz, 2H), 7.65 (m, J = 16.0, 4.9 Hz, Ts 2H), 7.53 (s, 1H), (m, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.09 (m, J = 9.3, 7.2 Hz, 1H), 4.68 (d, J = 6.9 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 164.3, 162.3, 155.6, 146.8, (d, J = 3.7 Hz), (d, J = 7.6 Hz), 133.6, 131.6, (d, J = 8.2 Hz), 130.0, 127.6, (d, J = 2.7 Hz), (d, J = 21.2 Hz), 114.6, (d, J = 22.9 Hz), 53.3, 51.7, F MR (471 MHz, CDCl 3 ) δ HRM Calculated for C 18 H 19 Cl 2 4 [M+a] , found F o-tolyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3ak. White solid (67% isolated yield), mp C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.53 (d, J = 0.5 Hz, 1H), (m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.29 Ts 7.23 (m, 5H), 4.68 (d, J = 18.6 Hz, 4H), 2.42 (s, 3H), 2.30 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 159.4, 146.0, 144.0, 143.5, 139.9, 135.7, 133.7, 130.8, 130.6, 123.0, 129.5, 128.5, 127.6, 125.9, 118.1, 53.4, 51.7, 21.5, HRM Calculated for C 21 H [M+H] , found (naphthalen-2-yl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c] pyridine 3al. White solid (69% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 2:1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.56 (s, 1H), 8.40 (d, J = 1.0 Hz, 1H), 8.05 (dd, J = 8.6, 1.7 Hz, 1H), (m, 2H), 7.85 (dd, J = 6.0, 3.4 Hz, 1H), 7.80 (d, J = 8.3 Hz, Ts 2H), 7.68 (s, 1H), (m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.70 (s, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 167.2, 156.9, 146.7, 144.1, 136.1, 133.7, 133.6, 133.5, 131.1, 130.0, 128.7, 128.6, 127.7, 127.6, 126.7, , , 124.4, 114.7, 53.4, 51.7, HRM Calculated for C 24 H [M+H] , found (pyridin-4-yl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3am. White solid (60% isolated yield), decompose at C. (eluent petroleum ether/ethyl acetate = 1: 2 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.71 (d, J = 5.9 Hz, 2H), 8.58 (s, 1H), 7.84 (d, J = 6.1 Hz, 2H), 7.79 (d, Ts J = 8.3 Hz, 2H), 7.63 (s, 1H), 7.34 (d, J = 8.0 Hz, 2H), 4.71 (d, J = 4.2 Hz, 4H), 2.41 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 154.1, 150.2, 147.1, 146.1, 144.5, 144.2, 133.6, , , 127.6, 121.1, 115.0, 53.3, 51.7, HRM Calculated for C 19 H [M+H] , found (benzo[d][1,3]dioxol-5-yl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3an. White solid (41% isolated yield) (eluent petroleum ether/ethyl acetate = 4 : 1 ). 1 H MR (500 MHz, CDCl 3 ) δ 8.46 (s, 1H), 7.78 (d, J = 8.3 Hz, 2H), 7.42 (dt, J = 8.1, 1.6 Hz, 3H), 7.33 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 8.1 Hz, 1H), 6.00 (s, 2H), 4.65 (dd, J = 8.2, 1.1 Hz, 4H), 2.41 (s, 3H). 13 Ts C MR (126 MHz, CDCl 3 ) δ 156.5, 148.7, 148.4, 146.6, 144.0, 143.8, 133.6, 133.3, 130.5, 123.0, 127.6, 121.0, 113.9, 108.5, 107.4, 101.4, 53.4, 51.6, HRM Calculated forc 21 H [M+a] , found

5 (4-fluorophenyl)-4,7-dimethyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine 3be. White solid (78% isolated yield) (eluent petroleum ether/ethyl acetate = 1:1) 1 H MR (500 MHz, CDCl 3 ) δ (m, 2H), (ddd, J = 15.9, 7.5, 6.7 Hz, 4H), (t, J = 8.8 Hz, 2H), 4.63 (dd, J = 14.9, 1.9 Hz, 4H), 2.42 (d, J = 4.8 Hz, 6H), 2.13 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) Ts δ 163.6, 161.7, 156.8, 149.5, 145.9, 144.0, 135.9, 133.8, (d, J = 8.2 Hz), 130.0, 129.2, 127.6, 122.9, (d, J = 21.5 Hz), 53.5, 52.7, 21.7, 21.5, F MR (471 MHz, CDCl 3 ) δ HRM Calculated for C 22 H 21 F 2 2 [M+a] , found F 3.16 diethyl 3-(4-fluorophenyl)-1,4-dimethyl-5H-cyclopenta[c]pyridine- 6,6(7H)-dicarboxylate 3ce. White solid (40% isolated yield) (eluent petroleum ether/ethyl acetate = 1:1) 1 H MR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 4.25 (q, J = 7.1 Hz, 4H), 3.59 (d, J = 15.8 Hz, 4H), 2.47 (s, 3H), 2.18 (s, 3H), 1.29 (t, J = 7.1 Hz, 6H). 13 C MR (126 MHz, CDCl 3 ) δ 171.4, 163.4, 161.5, 155.9, 150.5, 149.6, 136.7, 132.7, , , 124.2, 115.1, 114.9, 62.0, 59.5, 40.0, 39.0, 21.8, 16.1, F MR (471 MHz, CDCl 3 ) δ HRM Calculated for C 22 H 24 F 4 [M+H] , found Et 2 C Et 2 C '-(4-fluorophenyl)-1',4,4,4'-tetramethyl-5',7'-dihydrospiro[cyclohexane- 1,6'-cyclopenta[c]pyridine]-2,6-dione 3de. White solid (26% isolated yield) (eluent petroleum ether/ethyl acetate = 1:1 ) 1 H MR (500 MHz, CDCl 3 ) δ 7.41 (dd, J = 8.7, 5.5 Hz, 2H), H 7.09 (t, J = 8.8 Hz, 2H), 3.46 (s, 2H), 3.41 (s, 2H), 2.82 (d, J = C Hz, 2H), 2.67 (d, J = 14.3 Hz, 2H), 2.43 (s, 3H), 2.18 (s, 3H), 1.12 (s, 3H), 1.00 (s, 3H). 13 C MR (126 MHz, CDCl 3 ) δ 206.2, 163.4, 161.5, 156.1, 150.4, 150.0, 136.7, 131.5, , , 124.3, 115.1, 114.9, 70.2, 51.4, 39.11, 36.3, 30.6, 29.1, 27.7, 21.8, F MR (471 MHz, CDCl 3 ) δ (d, J = 4.5 Hz). HRM Calculated for C 23 H 24 F 2 [M+H] , found F F ,7-dimethyl-6-phenyl-1,3-dihydrofuro[3,4-c]pyridine 4ea. White solid (46% isolated yield) (eluent petroleum ether/diethyl ether= 4:1 ) 1 H MR (400 MHz, CDCl 3 ) δ (m, 5H), 5.14 (s, 2H), 5.09 (s, 2H), 2.44 (s, 3H), 2.14 (s, 3H). 13 C MR (101 MHz, CDCl 3 ) δ 157.3, 148.7, 147.9, 134.0, 131.5, 129.0, 128.0, 127.7, 121.6, 73.3, 72.8, 21.8, References (1) D. Llerena,. Buisine, C. Aubert, M. Malacria, Tetrahedron 1998, 54, (2) C. perger, L. H.. trand, A. Fiksdahl, Tetrahedron 2010, 66, (3) K.Tanaka,. uzuki, G. ishida, Eur. J. rg. Chem. 2006, (4) Y. Yamamoto, K. Kinpara, H. ishiyama, K. Itoh, Adv. ynth. Catal. 2005, 347, (5) Y. Yamamoto, K. Kinpara, R. gawa, H. ishiyama, Itoh. K, Chem. Eur. J. 2006, 12, (6) M. Y. Wani, F. Athar, A. alauddin,. M. Agarwal, A. Azam, I. Choi, A. R. Bhat, Eur. J. Med. Chem. 2011, 46, (7) A. Kocak, G.Ahmetli,. Kocak,. Malkondu, A. Yaylaci,. Kurbanli, ynth. Commun. 2011, 41, (8) H. harghi, M. H. arvari, ynlett 2001, 1, Copy of MR ( 1 H, 13 C, HMBC) pectra 6. Copy of HRM pectra 5

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