Supporting Information

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1 Supporting Information Synthesis of 2-Benzazepines from Benzylamines and MBH Adducts Under Rhodium(III) Catalysis via C(sp 2 ) H Functionalization Ashok Kumar Pandey, a Sang Hoon Han, a Neeraj Kumar Mishra, a Dahye Kang, b,c Suk Hun Lee, a Rina Chun, a Sungwoo Hong, b,c, * Jung Su Park, d, * and In Su Kim a, * a School of Pharmacy, Sungkyunkwan University, Suwon 16419, Republic of Korea b Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea c Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea d Department of Chemistry, Sookmyung Women s University, Seoul 04310, Republic of Korea * Corresponding authors. hongorg@kaist.ac.kr (S.Hong), jspark@sookmyung.ac.kr (J.S.Park), insukim@skku.edu (I.S.Kim) List of the Contents General methods S3 Optimization for reaction conditions S4 S5 General procedure for the synthesis of 2-benzazepines (3a 3q, 5a 5g, 7a and 7b) S6 Characterization data for products (3a 3q, 5a 5g, 7a and 7b) S7 S19 Experimental procedure and characterization data for the synthesis of secondary benzylamine (8a) S20 Experimental procedure and characterization data for the synthesis of N,N-diallylated benzylamine (8e) S21 S1

2 Experimental procedure and characterization data for the synthesis of N-allylated compounds (9b 9d) S22 S23 Experimental procedure and characterization data for the synthesis of compound 12a S24 Determination of enantiomeric excess of chiral products 5a and 5d S25 S26 Computational details S27 S52 References S53 X-ray crystallographic data of compound 3o S54 S62 1 H NMR and 13 C NMR spectra of all compounds S63 S94 S2

3 General methods Commercially available reagents were used without additional purification, unless otherwise stated. Morita-Baylis-Hillman adducts (2a 2d) and 8d were prepared according to reported literature. 1,2 Sealed tubes ( mm 2 ) were purchased from Fischer Scientific and dried in oven for overnight and cooled at room temperature prior to use. Thin layer chromatography was carried out using plates coated with Kieselgel 60 F 254 (Merck). For flash column chromatography, E. Merck Kieselgel 60 ( mesh) was used. Nuclear magnetic resonance spectra ( 1 H and 13 C NMR) were recorded on a Bruker Unity 400 spectrometers in CDCl 3 solution and chemical shifts are reported as parts per million (ppm). Resonance patterns are reported with the notations s (singlet), d (doublet), t (triplet), q (quartet), and m (multiplet). Coupling constants (J) are reported in hertz (Hz). IR spectra were recorded on a Varian 2000 Infrared spectrophotometer and are reported as cm -1. High-resolution mass spectra (HRMS) were recorded on a JEOL JMS-600 spectrometer. S3

4 Optimization for reaction conditions Table S1. Screening of catalysts a entry catalyst (mol%) additive (mol %) yield b 1 [Ru(p-cymene)Cl 2 ] 2 (2.5) AgSbF 6 (10), Cu(OAc) 2 (70) 50 2 [IrCp*Cl 2 ] 2 (2.5) AgSbF 6 (10), Cu(OAc) 2 (70) 35 3 [CoCp*(CO)I 2 ] (5) AgSbF 6 (20), Cu(OAc) 2 (70) N.R. a Reaction conditions: 1a (0.2 mmol), 2a (0.6 mmol), DCE (1 ml) under air at 110 o C in pressure tubes. b Isolated percent yield by flash column chromatography. S4

5 Table S2. Screening of solvents a entry solvent yield b 1 DCE 72 2 DCM 64 3 CH 3 CN trace 4 THF 30 5 TFE 40 a Reaction conditions: 1a (0.2 mmol), 2a (0.6 mmol), solvent (1 ml) under air at 110 o C in pressure tubes. b Isolated percent yield by flash column chromatography. S5

6 General procedure for the synthesis of 2-benzazepines (3a 3q, 5a 5g, 7a and 7b) To an oven-dried sealed tube charged with phenylmethanamine (1a) (21.4 mg, 0.2 mmol, 100 mol %), [RhCp*Cl 2 ] 2 (3.1 mg, mmol, 2.5 mol %), AgSbF 6 (6.9 mg, 0.02 mmol, 10 mol %), Cu(OAc) 2 (25.4 mg, 0.14 mmol, 70 mol %) and methyl 2-(acetoxymethyl)acrylate (2a) (94.8 mg, 0.6 mmol, 300 mol %) was added DCE (1 ml) under air at room temperature. The reaction mixture was allowed to stir at 110 C for 10 min. The reaction mixture was cooled to room temperature, diluted with EtOAc (3 ml) and concentrated in vacuo. The residue was purified by flash column chromatography (n-hexanes/etoac = 4:1) to afford 3a (43.3 mg, 71%) as sticky yellow oil. S6

7 Characterization data for products (3a 3q, 5a 5g, 7a and 7b) Methyl 2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-carboxylate (3a) 43.3 mg (72%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (s, 1H), 7.39 (dd, J = 6.6, 2.2 Hz, 1H), (m, 3H), 7.13 (dd, J = 6.6, 2.2 Hz, 1H), 6.22 (s, 1H), 5.63 (s, 1H), 3.98 (s, 2H), 3.90 (s, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.31 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.2, 167.3, 140.5, 139.9, 137.5, 134.1, 133.3, 131.4, 129.4, 129.3, 127.4, 126.8, 58.7, 55.7, 53.4, 52.1, 51.9; IR (KBr) υ 3062, 3027, 2950, 2928, 2849, 1716, 1634, 1436, 1307, 1256, 1153, 1114, 815, 740, cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 19 NO 4 [M] , found Methyl carboxylate (3b) 7-methoxy-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine mg (54%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 (s, 1H), 7.04 (d, J = 8.4 Hz, 1H), 6.91 (d, J = 2.4 Hz, 1H), 6.80 (dd, J = 8.0, 2.4 Hz, 1H), 6.22 (s, 1H), 5.64 (s, 1H), 3.89 (s, 2H), 3.84 (s, 2H), 3.80 (s, 3H), 3.79 (s, 3H), 3.74 (s, 3H), 3.28 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.1, 167.3, 158.7, 140.0, 137.5, 135.2, 132.5, 131.8, 130.6, 126.9, 118.1, 114.7, 57.7, 55.3, 55.2, 53.4, 52.1, 51.8; IR (KBr) υ 3053, 2954, 2925, 2854, 1718, 1636, 1436, 1328, 1267, 1165, 1122, 836, 738 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 5 [M] , found S7

8 Methyl carboxylate (3c) 41.0 mg (65%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.69 (s, 1H), 7.20 (s, 1H), 7.08 (d, J = 7.7 Hz, 1H), 7.01 (d, J = 7.6 Hz, 1H), 6.21 (s, 1H), 5.62 (s, 1H), 3.94 (s, 2H), 3.88 (s, 2H), 3.79 (s, 3H), 3.75 (s, 3H), 3.28 (s, 2H), 2.34 (s, 3H); 13 C NMR (100 MHz, CDCl 3 )δ 168.1, 167.3, 140.1, 137.6, 137.5, 136.9, 134.0, 133.9, 131.2, 130.1, 130.1, 129.4, 126.7, 58.3, 55.6, 53.3, 52.0, 51.8, 20.9; IR (KBr) υ 2992, 2950, 2921, 1717, 1631, 1434, 1244, 1227, 1197, 1063, 817 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 4 [M] , found Methyl carboxylate (3d) 44.2 mg (66%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.63 (d, J = 1.6 Hz, 1H), 7.37 (d, J = 2.2 Hz, 1H), 7.22 (dd, J = 8.0, 2.2 Hz, 1H), 7.06 (d, J = 8.0 Hz, 1H), 6.22 (s, 1H), 5.63 (s, 1H), 3.92 (s, 2H), 3.88 (s, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.29 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 167.2, 138.8, 138.4, 137.4, 135.7, 133.1, 133.0, 132.6, 130.7, 129.0, 126.9, 57.9, 55.7, 53.5, 52.2, 51.9; IR (KBr) υ 2950, 2847, 1715, 1435, 1247, 1196, 1153, 1062, 817 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 ClNO 4 [M] , found Methyl carboxylate (3e) 2-(2-(methoxycarbonyl)allyl)-7-methyl-2,3-dihydro-1H-benzo[c]azepine-4-7-chloro-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-7-bromo-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4- S8

9 55.3 mg (73%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.62 (s, 1H), 7.52 (d, J = 1.9 Hz, 1H), 7.37 (dd, J = 8.1, 2.0 Hz, 1H), 6.99 (d, J = 8.0 Hz, 1H), 6.22 (s, 1H), 5.62 (s, 1H), 3.91 (s, 2H), 3.89 (s, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.28 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 167.2, 139.5, 138.2, 137.4, 136.0, 135.6, 133.2, 131.9, 130.9, 126.8, 120.9, 58.1, 55.8, 53.5, 52.2, 51.9; IR (KBr) υ 3026, 2998, 2950, 2848, 1717, 1634, 1435, 1262, 1152, 1117, 954, 817, 749 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 BrNO 4 [M] , found Dimethyl 2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4,7-dicarboxylate (3f) 57.4 mg (80%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 8.07 (s, 1H), 7.91 (d, J = 7.9 Hz, 1H), 7.76 (s, 1H), 7.21 (d, J = 7.8 Hz, 1H), 6.22 (s, 1H), 5.62 (s, 1H), 4.02 (s, 2H), 3.92 (s, 5H), 3.81 (s, 3H), 3.75 (s, 3H), 3.30 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.8, 167.2, 166.4, 145.7, 138.8, 137.4, 134.4, 134.2, 132.7, 130.2, 129.5, 129.5, 126.8, 58.6, 56.0, 53.5, 52.2, 52.2, 51.9; IR (KBr) υ 3060, 2951, 1722, 1633, 1435, 1287, 1198, 1060, 759 cm -1 ; HRMS (quadrupole, EI) calcd for C 19 H 21 NO 6 [M] , found Methyl carboxylate (3g) 2-(2-(methoxycarbonyl)allyl)-9-methyl-2,3-dihydro-1H-benzo[c]azepine-4- S9

10 34.1 mg (54%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (s, 1H), (m, 3H), 6.25 (s, 1H), 5.71 (s, 1H), 3.84 (s, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.72 (s, 2H), 3.37 (s, 2H), 2.33 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.9, 167.3, 141.5, 141.4, 137.7, 136.4, 135.3, 133.7, 131.5, 130.5, 130.3, 126.9, 54.6, 54.1, 53.1, 52.1, 51.8, 20.1; IR (KBr) υ 2950, 2849, 1714, 1632, 1617, 1434, 1263, 1204, 1073, 788 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 4 [M] , found Methyl carboxylate (3h) 25.8 mg (39%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.77 (s, 1H), (t, J = 8.0 Hz, 1H), 6.98 (d, J = 7.6 Hz, 1H), 6.89 (d, J = 8.4 Hz, 1H), 6.28 (s, 1H), 5.73 (s, 1H), 4.01 (s, 2H), 3.84 (s, 3H), 3.83 (s, 3H), 3.78 (s, 3H), 3.75 (s, 2H), 3.37 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.9, 167.3, 157.2, 140.8, 137.5, 136.2, 131.4, 128.5, 127.6, 126.8, 124.9, 111.5, 55.8, 54.5, 54.4, 52.0, 51.8, 49.5; IR (KBr) υ 2950, 2840, 1718, 1436, 1261, 1199, 1097, 815, 757 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 5 [M] , found Methyl carboxylate (3i) 9-methoxy-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-9-fluoro-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4- S10

11 F N CO 2 Me CO 2 Me 3i 39.6 mg (62%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (s, 1H), (m, 1H), 7.16 (d, J = 7.2 Hz, 1H), 7.01 (t, J = 8.8 Hz, 1H), 6.25 (s, 1H), 5.66 (s, 1H), 4.01 (s, 2H), 3.85 (s, 2H), 3.80 (s, 3H), 3.75 (s, 3H), 3.33 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 167.2, (d, J C-F = Hz), 139.2, 137.3, (d, J C-F = 3.8 Hz), 132.5, (d, J C-F = 3.1 Hz), (d, J C-F = 9.1 Hz), (d, J C-F = 15.5 Hz), (d, J C-F = 23.9 Hz), 55.6, 54.0, 52.2, 51.9, 48.9 (d, J C-F = 6.9 Hz); IR (KBr) υ 2952, 2919, 2850, 1718, 1634, 1436, 1262, 1159, 794 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 FNO 4 [M] , found Methyl carboxylate (3j) 42.2 mg (63%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (s, 1H), 7.34 (dd, J = 7.9, 1.5 Hz, 1H), (m, 1H), 7.21 (d, J = 7.8 Hz, 1H), 6.28 (s, 1H), 5.71 (s, 1H), 4.09 (s, 2H), 3.81 (s, 3H), 3.77 (s, 2H), 3.75 (s, 3H), 3.38 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.6, 167.2, 139.6, 137.2, 136.7, 134.2, 132.5, 131.4, 130.2, 128.0, 127.0, 111.5, 55.0, 54.6, 53.7, 52.2, 51.9; IR (KBr) υ 3069, 2994, 2951, 2927, 1718, 1436, 1261, 1194, 1155, 1065, 788 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 ClNO 4 [M] , found Methyl 9-chloro-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-2-(2-(methoxycarbonyl)allyl)-8-methyl-2,3-dihydro-1H-benzo[c]azepine-4- carboxylate (3k) S11

12 40.3 mg (64%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.71 (s, 1H), 7.28 (d, J = 7.9 Hz, 1H), 7.08 (d, J = 7.8 Hz, 1H), 6.94 (s, 1H), 6.22 (s, 1H), 5.64 (s, 1H), 3.96 (s, 2H), 3.89 (s, 2H), 3.79 (s, 3H), 3.75 (s, 3H), 3.30 (s, 2H), 2.33 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 167.3, 140.4, 140.0, 139.8, 137.5, 133.5, 131.3, 130.2, 130.1, 128.1, 126.9, 58.8, 55.5, 53.2, 52.0, 51.9, 21.3; IR (KBr) υ 2949, 2924, 2850, 1702, 1607, 1434, 1252, 1194, 1064, 818 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 4 [M] , found Methyl carboxylate (3l) 30.1 mg (45%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.69 (s, 1H), 7.32 (d, J = 8.2 Hz, 1H), (dd, J = 8.2, 2.2 Hz, 2H), 7.15 (d, J = 2.1 Hz, 1H), 6.27 (s, 1H), 5.70 (s, 1H), 3.95 (s, 2H), 3.90 (s, 2H), 3.80 (s, 3H), 3.76 (s, 3H), 3.34 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 167.1, 141.7, 139.0, 136.7, 135.3, 134.4, 132.7, 131.4, 129.5, 127.7, 58.0, 55.1, 53.2, 52.2, 52.0; IR (KBr) υ 2952, 2925, 2850, 1717, 1436, 1267, 1195, 977, 822, 739 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 ClNO 4 [M] , found Methyl carboxylate (3m) 8-chloro-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-8-bromo-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4- S12

13 43.2 mg (57%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.64 (s, 1H), 7.40 (dd, J = 8.2, 2.1 Hz, 1H), 7.27 (d, J = 2.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H), 6.23 (s, 1H), 5.64 (s, 1H), 3.93 (s, 2H), 3.88 (s, 2H), 3.79 (s, 3H), 3.75 (s, 3H), 3.29 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.9, 167.2, 142.6, 138.6, 137.3, 134.8, 132.9, 132.2, 132.1, 130.5, 126.9, 123.6, 58.3, 55.8, 53.3, 52.2, 51.9; IR (KBr) υ 2950, 2917, 2850, 1716, 1633, 1434, 1247, 1196, 957, 819, 736 cm - 1 ; HRMS (quadrupole, EI) calcd for C 17 H 18 BrNO 4 [M] , found carboxylate (3n) 44.3 mg (60%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.72 (s, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.36 (s, 1H), 6.23 (s, 1H), 5.63 (s, 1H), 4.01 (s, 2H), 3.91 (s, 2H), 3.81 (s, 3H), 3.74 (s, 3H), 3.30 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 167.2, 141.4, 138.0, (q, J C-F = 1.2 Hz), 134.2, 133.4, (q, J C-F = 34.0 Hz), 126.8, (q, J C- F = 3.7 Hz), (q, J C-F = Hz), (q, J C-F = 3.9 Hz), 122.4, 58.4, 55.8, 53.7, 52.3, 51.9; IR (KBr) υ 3060, 2927, 1716, 1437, 1329, 1271, 1165, 1123, 955, 712 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 18 F 3 NO 4 [M] , found Methyl Methyl 2-(2-(methoxycarbonyl)allyl)-8-(trifluoromethyl)-2,3-dihydro-1H-benzo[c]azepine- 7-(2-(methoxycarbonyl)allyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':3,4]benzo[1,2- c]azepine-9-carboxylate (3o) S13

14 49.7 mg (72%, C2:C4 = 5:1); white solid; mp C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (s, 1H), 6.68 (d, J = 7.8 Hz, 1H), 6.55 (d, J = 7.7 Hz, 1H), 6.21 (d, J = 1.7, 1H), 6.02 (s, 2H), 5.64 (d, J = 1.6 Hz, 1H), 3.92 (s, 4H), 3.79 (s, 3H), 3.75 (s, 3H), 3.29 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.0, 167.3, 147.9, 146.5, 137.6, 134.3, 132.0, 130.5, 126.7, 121.6, 116.6, 108.7, 101.4, 58.3, 56.2, 52.9, 52.1, 51.9; IR (KBr) υ 2950, 2903, 2849, 1702, 1636, 1440, 1251, 1165, 1055, 927, 814 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 19 NO 6 [M] , found Benzyl 2-(2-((benzyloxy)carbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-carboxylate (3p) 54.8 mg (60%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.68 (s, 1H), (m, 10H), (m, 3H), (m, 1H), 6.16 (s, 1H), 5.54 (s, 1H), 5.15 (s, 2H), 5.10 (s, 2H), 3.86 (s, 2H), 3.84 (s, 2H), 3.24 (s, 2H); 13 C NMR (100 MHz, CDCl 3 )δ 167.5, 166.7, 140.6, 140.2, 137.6, 136.1, 136.0, 134.0, 133.3, 131.5, 129.4, 129.3, 128.6, 128.5, 128.3, 128.2, 128.1, 127.9, 127.4, 126.9, 66.7, 66.4, 58.6, 55.9, 53.6; IR (KBr) υ 3060, 3031, 2924, 1718, 1632, 1455, 1241, 1193, 1162, 752 cm -1 ; HRMS (quadrupole, EI) calcd for C 29 H 27 NO 4 [M] , found S14

15 tert-butyl (3q) 2-(2-(tert-butoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-carboxylate 36.5 mg (47%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.62 (s, 1H), 7.35 (d, J = 6.8 Hz, 1H), (m, 2H), 7.09 (d, J = 6.8 Hz, 1H), 6.12 (s, 1H), 5.56 (s, 1H), 3.91 (s, 2H), 3.83 (s, 2H), 3.28 (s, 2H), 1.52 (s, 9H), 1.46 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.9, 166.2, 140.5, 139.3, 138.6, 134.3, 133.4, 133.0, 129.1, 128.9, 127.2, 125.3, 80.8, 80.6, 58.6, 56.3, 53.9, 28.2, 28.1; IR (KBr) υ 2975, 2928, 1706, 1633, 1366, 1252, 1150, 848, 765 cm -1 ; HRMS (quadrupole, EI) calcd for C 23 H 31 NO 4 [M] , found Methyl carboxylate (5a) 44.1 mg (70%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.7 (s, 1H), 7.43 (dd, J = 5.6, 3.5 Hz, 1H), 7.3 (m, 2H), 7.15 (dd, J = 5.5, 3.5 Hz, 1H), 6.16 (s, 1H), 5.61 (s, 1H), 4.10 (q, J = 6.9 Hz, 1H), 4.00 (d, J = 19.8 Hz, 1H), 3.89 (d, J = 19.8 Hz, 1H), 3.79 (s, 3H), 3.72 (s, 3H), 3.13 (s, 2H), 1.34 (d, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 167.4, 147.2, 139.4, 138.0, 134.8, 132.2, 132.0, 129.2, 128.6, 127.0, 126.1, 61.9, 53.1, 52.0, 51.8, 48.9, 20.6; IR (KBr) υ 2955, 2870, 1718, 1634, 1436, 1264, 1195, 1151, 953, 738 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 4 [M] , found Methyl carboxylate (5b) (R)-2-(2-(methoxycarbonyl)allyl)-1-methyl-2,3-dihydro-1H-benzo[c]azepine-4-1-ethyl-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4- S15

16 51.3 mg (78%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (s, 1H), (m, 1H), (m, 2H), (m, 1H), 6.23 (s, 1H), 5.70 (s, 1H), 4.05 (dd, J = 19.9, 2.3 Hz, 1H), 3.92 (d, J = 19.9 Hz, 1H), 3.86 (s, 3H), 3.84 (d, J = 7.4 Hz, 1H), 3.79 (s, 3H), 3.22 (d, J = 3.3 Hz, 2H), 1.82 (dt, J = 14.5, 7.3 Hz, 1H), 1.63 (dt, J = 14.0, 7.1 Hz, 1H), 1.00 (t, J = 7.3 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 167.5, 146.2, 139.4, 138.2, 134.8, 132.3, 132.0, 129.6, 128.9, 126.9, 125.7, 68.6, 53.4, 52.0, 51.7, 48.8, 26.9, 11.0; IR (KBr) υ 2951, 2876, 1717, 1635, 1453, 1255, 1195, 1059, 816, 769 cm -1 ; HRMS (quadrupole, EI) calcd for C 19 H 23 NO 4 [M] , found Methyl carboxylate (5c) 1-benzyl-2-(2-(methoxycarbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine mg (30%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.8 (s, 1H), 7.46 (d, J = 7.6 Hz, 1H), (m, 5H), 7.04 (d, J = 7.2 Hz, 2H), 6.79 (d, J = 7.5 Hz, 1H), 6.13 (s, 1H), 5.52 (s, 1H), 4.26 (t, J = 7.7 Hz, 1H), 4.04 (d, J = 19.6 Hz, 1H), 3.84 (d, J = 19.4 Hz, 1H), 3.81 (s, 3H), 3.71 (s, 3H), 3.19 (s, 2H), 3.08 (dd, J = 14.0, 7.8 Hz, 1H), 2.86 (dd, J = 13.9, 7.7 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 167.5, 144.9, 139.5, 138.5, 137.8, 134.9, 132.4, 132.2, 129.7, 129.2, 128.8, 128.0, 127.1, 126.1, 126.0, 68.0, 53.5, 52.1, 51.7, 49.2, 40.0; IR (KBr) υ 3059, 3024, 2923, 2852, 1718, 1634, 1435, 1241, 1195, 1125, 1065, 950, 768 cm -1 ; HRMS (quadrupole, EI) calcd for C 24 H 25 NO 4 [M] , found S16

17 dihydro-1h-benzo[c]azepine-4-carboxylate (5d) 38.3 mg (43%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.67 (s, 1H), 7.41 (d, J = 6.9 Hz, 1H), (m, 2H), 7.17 (d, J = 6.8 Hz, 1H), 6.18 (s, 1H), 5.68 (s, 1H), 4.06 (t, J = 6.8 Hz, 1H), 4.00 (dd, J = 19.9, 2.4 Hz, 1H), (m, 2H), 3.79 (s, 3H), 3.70 (s, 3H), 3.26 (d, J = 14.8 Hz, 1H), 3.20 (d, J = 15.6 Hz, 1H), 0.80 (s, 9H), (d, J = 4.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 )δ 168.2, 167.4, 143.2, 139.5, 137.8, 134.7, 132.8, 132.2, 130.4, 128.8, , 126.0, 68.4, 64.8, 53.9, 52.0, 51.7, 50.0, 25.7, 18.1, -5.6, -5.7; IR (KBr) υ 2951, 2927, 2854, 1718, 1635, 1434, 1255, 1195, 1105, 836, 771 cm -1 ; HRMS (quadrupole, EI) calcd for C 24 H 35 NO 5 Si [M] , found Methyl carboxylate (5e) Methyl (R)-1-(((tert-butyldimethylsilyl)oxy)methyl)-2-(2-(methoxycarbonyl)allyl)-2,3-2-(2-(methoxycarbonyl)allyl)-1-phenyl-2,3-dihydro-1H-benzo[c]azepine mg (62%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.76 (d, J = 2.4 Hz, 1H), 7.54 (d, J = 7.6 Hz, 1H), (m, 2H), (m, 3H), 7.14 (d, J = 7.5 Hz, 1H), 6.99 (d, J = 7.3 Hz, 2H), 6.23 (s, 1H), 5.72 (s, 1H), 5.27 (s, 1H), 3.79 (s, 3H), 3.73 (d, J = 6.9 Hz, 1H), 3.71 (s, 3H), 3.37 (s, 2H), 3.23 (d, J = 17.5 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.1, 167.5, 142.8, 141.8, 140.0, 138.0, 134.7, 133.8, 132.4, 130.8, 129.3, 128.8, 128.3, 127.5, 127.2, 126.0, 70.7, 53.0, 52.0, 51.8, 48.1; IR (KBr) υ 3062, 2925, 2853, 1716, 1676, 1599, 1257, 1168, 1030, 758 cm -1 ; HRMS (quadrupole, EI) calcd for C 23 H 23 NO 4 [M] , found S17

18 Methyl carboxylate (5f) 29.6 mg (45%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.75 (s, 1H), (m, 1H), (m, 1H), 7.28 (dd, J = 8.8, 4.4 Hz, 2H), 6.21 (s, 1H), 5.88 (s, 1H), 3.94 (s, 2H), 3.78 (s, 3H), 3.68 (s, 3H), 2.93 (s, 2H), 1.49 (s, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 167.5, 150.5, 140.5, 138.9, 135.9, 132.2, 132.1, 129.1, 126.8, 126.5, 125.7, 60.4, 52.0, 51.6, 49.3, 49.2, 28.6; IR (KBr) υ 2978, 2950, 2923, 2852, 1715, 1634, 1435, 1288, 1244, 1191, 757 cm -1 ; HRMS (quadrupole, EI) calcd for C 19 H 23 NO 4 [M] , found Methyl carboxylate (5g) 2-(2-(methoxycarbonyl)allyl)-1,1-dimethyl-2,3-dihydro-1H-benzo[c]azepine-4-1-(2-(methoxycarbonyl)allyl)-1,2,8,9,10,10a-hexahydronaphtho[1,8-bc]azepine-3- N CO 2 Me CO 2 Me 5g 21.1 mg (31%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 )δ 7.73 (s, 1H), (m, 2H), 7.08 (d, J = 7.5 Hz, 1H), 6.21 (s, 1H), 5.86 (s, 1H), 4.01 (t, J = 7.6 Hz, 1H), 3.95 (d, J = 18.7 Hz, 1H), 3.78 (s, 3H), 3.72 (s, 3H), 3.65 (d, J = 18.7 Hz, 1H), 3.13 (d, J = 15.8 Hz, 1H), 2.99 (d, J = 15.8 Hz, 1H), (m, 2H), 2.03 (m, 1H), 1.93 (m, 1H), 1.83 (q, J = 11.5 Hz, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.5, 167.5, 141.0, 139.6, 139.1, 138.8, 134.7, 131.5, 131.1, 130.7, 126.5, 126.3, 60.4, 53.3, 52.0, 51.7, 48.0, 30.7, 30.3, 21.5; IR (KBr) υ 2922, 2854, 1702, 1633, 1433, 1255, 1207, 1123, 1072, 743 cm -1 ; HRMS (quadrupole, EI) calcd for C 20 H 23 NO 4 [M] , found S18

19 Methyl (E)-3-(2-(methoxycarbonyl)allyl)-1,2,3,4-tetrahydrobenzo[d]azocine-5-carboxylate (7a) CO 2 Me N CO 2 Me 7a 7.6 mg (12%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (s, 1H), (m, 1H), 7.21 (d, J = 4.4 Hz, 2H), 7.15 (d, J = 7.2 Hz, 1H), 6.09 (s, 1H), 5.45 (s, 1H), 3.79 (s, 3H), 3.64 (s, 3H), 3.44 (s, 2H), 3.35 (s, 2H), (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.8, 167.3, 139.5, 139.4, 135.5, 134.2, 131.8, 129.4, 129.0, 128.8, 126.4, 125.9, 58.4, 56.6, 54.7, 52.0, 51.7, 33.8; IR (KBr) υ 2924, 2851, 1717, 1637, 1436, 1249, 1195, 1131, 953, 737 cm - 1 ; HRMS (quadrupole, EI) calcd for C 18 H 21 NO 4 [M] , found Dimethyl 2,2'-((phenethylazanediyl)bis(methylene))diacrylate (7b) 29.2 mg (46%); sticky colorless oil; 1 H NMR (400 MHz, CDCl 3 )δ (m, 5H), 6.28 (s, 2H), 5.79 (s, 2H), 3.82 (s, 6H), 3.43 (s, 4H), (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.3, 140.3, 138.0, 128.9, 128.2, 126.1, 125.9, 56.0, 54.5, 51.7, 33.8; IR (KBr) υ 3026, 2950, 2848, 1717, 1634, 1435, 1309, 1262, 1152, 1117, 954, 749, 700 cm -1 ; HRMS (quadrupole, EI) calcd for C 18 H 23 NO 4 [M] , found S19

20 Experimental procedure and characterization data for the synthesis of secondary benzylamine (8a) To an oven-dried round bottom flask (100 ml) charged with phenylmethanamine (1a) (117.7 mg, 1.1 mmol, 110 mol %) was added CH 2 Cl 2 (20 ml) under air at room temperature. The reaction mixture was allowed to stir at room temperature. The solution of methyl 2- (acetoxymethyl)acrylate (2a) (152 mg, 1 mmol, 100 mol %) in CH 2 Cl 2 (2 ml) was added dropwise in the reaction mixture. The reaction mixture was allowed to stir for 1 h at room temperature. The organic solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography (n-hexanes/etoac = 1:1) to afford 8a (92.3 mg, 45%) as colorless oil. The characterization data of 8a was full agreement with the reported literature. 3 S20

21 Experimental procedure and characterization data for the synthesis of N,N - diallylated benzylamine (8e) To an oven-dried round bottom flask (50 ml) charged with phenylmethanamine (1a) (107 mg, 1 mmol, 100 mol %), K 2 CO 3 (207 mg, 1.5 mmol, 150 mol %) was added CH 2 Cl 2 (10 ml) under air at room temperature. The solution of methyl 2-(acetoxymethyl)acrylate (2a) (331.8 mg, 2.1 mmol, 210 mol %) in CH 2 Cl 2 (1 ml) was added drop-wise in the reaction mixture. The reaction mixture was allowed to stir for 1 h at room temperature. The solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography (n-hexanes/etoac = 6:1) to afford 8e (0.26 g, 87%) as colorless oil. Dimethyl 2,2'-((benzylazanediyl)bis(methylene))diacrylate (8e) 0.26 g (87%); sticky colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 6.27 (s, 2H), 5.94 (s, 2H), 3.72 (s, 6H), 3.61 (s, 2H), 3.30 (s, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.3, 139.1, 137.9, 128.4, 128.2, 126.9, 126.1, 58.3, 54.3, 51.7; IR (KBr) υ 2998, 2950, 2840, 1704, 1633, 1434, 1246, 1195, 1162, 1110, 816, 767 cm -1 ; HRMS (quadrupole, EI) calcd for C 17 H 21 NO 4 [M] , found S21

22 Experimental procedure and characterization data for the synthesis of N- allylated compounds (9b 9d) To an oven-dried sealed tube charged with N-methyl-1-phenylmethanamine (1a) (24.2 mg, 0.2 mmol, 100 mol %), [RhCp*Cl 2 ] 2 (3.1 mg, mmol, 2.5 mol %), AgSbF 6 (6.9 mg, 0.02 mmol, 10 mol %), Cu(OAc) 2 (25.4 mg, 0.14 mmol, 70 mol %) and methyl 2- (acetoxymethyl)acrylate (2a) (63.2 mg, 0.4 mmol, 200 mol %) was added DCE (1 ml) under air at room temperature. The reaction mixture was allowed to stir at 110 C for 10 min. The reaction mixture was cooled to room temperature, diluted with EtOAc (3 ml) and concentrated in vacuo. The residue was purified by flash column chromatography (n-hexanes/etoac = 4:1) to afford 9b (41.2 mg, 94%) as sticky colorless oil. Methyl 2-((benzyl(methyl)amino)methyl)acrylate (9b) 41.2 mg (94%); sticky colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 6.31 (d, J = 1.9 Hz, 1H), 5.88 (d, J = 1.7 Hz, 1H), 3.78 (s, 3H), 3.58 (s, 2H), 3.26 (s, 2H), 2.23 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.5, 139.1, 137.9, 128.8, 128.2, 126.9, 126.5, 62.1, 57.6, 51.8, 42.2; IR (KBr) υ 3062, 3027, 2949, 28.39, 2789, 1718, 1634, 1453, 1436, 1268, 1151, 1025, 738 cm -1 ; HRMS (quadrupole, EI) calcd for C 13 H 17 NO 2 [M] , found Methyl 2-((benzyl(isopropyl)amino)methyl)acrylate (9c) 34.6 mg (70%); sticky colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 6.20 (d, J = 1.5 Hz, 1H), 5.93 (d, J = 1.9 Hz, 1H), 3.72 (s, 3H), 3.58 (s, 2H), 3.27 (s, 2H), (m, 1H), 1.03 (d, J = 6.6 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.7, 140.7, 139.3, 128.3, S22

23 128.1, 126.6, 125.4, 53.7, 51.6, 49.5, 49.0, 17.7; IR (KBr) υ 3062, 3026, 2963, 2931, 2828, 1718, 1435, 1262, 1165, 1139, 1102, 956 cm -1 ; HRMS (quadrupole, EI) calcd for C 15 H 21 NO 2 [M] , found Methyl 2-((allyl(benzyl)amino)methyl)acrylate (9d) N MeO 2 C 9d 35.3 mg (75%); yellow sticky oil; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), 6.25 (s, 1H), 5.90 (s, 1H), (m, 1H), 5.19 (d, J = 17.2 Hz, 1H), 5.12 (d, J = 10.2 Hz, 1H), 3.72 (s, 3H), 3.58 (s, 2H), 3.28 (s, 2H), 3.05 (d, J = 6.1 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.5, 139.4, 138.3, 135.7, 128.6, 128.2, 126.9, 126.0, 117.3, 57.9, 56.5, 53.8, 51.7; IR (KBr) υ 3063, 3027, 2949, 2927, 2797, 1719, 1636, 1436, 1305, 1260, 1150, 1116, 920 cm -1 ; HRMS (quadrupole, EI) calcd for C 15 H 19 NO 2 [M] , found S23

24 Experimental procedure and characterization data for the synthesis of compound (12a) To an oven-dried sealed tube charged with [RhCp*Cl 2 ] 2 (3.1 mg, mmol, 2.5 mol %), AgSbF 6 (6.9 mg, 0.02 mmol, 10 mol %), Cu(OAc) 2 (25.4 mg, 0.14 mmol, 70 mol %), benzyl 2-(acetoxymethyl)acrylate (2b) (93.6 mg, 0.4 mmol, 200 mol %) and methyl 2- ((benzylamino)methyl)acrylate (8a) (41.0 mg, 0.2 mmol, 100 mol %) was added DCE (1 ml) under air at room temperature. The reaction mixture was allowed to stir at 110 C for 10 min. The reaction mixture was cooled to room temperature and purified by flash column chromatography (n-hexanes/etoac = 4:1) to afford 12a (22.6 mg, 30%) as sticky yellow oil. Methyl (12a) 2-(2-((benzyloxy)carbonyl)allyl)-2,3-dihydro-1H-benzo[c]azepine-4-carboxylate 22.6 mg (30%); sticky yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.64 (s, 1H), (m, 6H), (m, 2H), 7.01 (d, J = 6.8 Hz, 1H), 6.18 (s, 1H), 5.57 (s, 1H), 5.10 (s, 2H), 3.86 (s, 2H), 3.80 (s, 2H), 3.70 (s, 3H), 3.25 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.1, 166.6, 140.4, 140.0, 137.5, 136.0, 134.1, 133.2, 131.3, 129.4, 129.4, 128.5, 128.1, 128.0, 127.4, 127.2, 66.4, 58.6, 55.7, 53.6, 52.1; IR (KBr) υ 3063, 3032, 2949, 2842, 1708, 1632, 1434, 1245, 1195, 1160, 1063, 959 cm -1 ; HRMS (quadrupole, EI) calcd for C 23 H 23 NO 4 [M] , found S24

25 Determination of enantiomeric excess of chiral products 5a and 5d HPLC condition for 5a: Chiralpak IA column, hexanes:i-proh = 70:30, 1.0 ml/min, 220 nm, t minor = 4.2 min, t major = 5.0 min, ee = 99%. < HPLC chromatogram of racemic 5a > < HPLC chromatogram of chiral 5a > S25

26 HPLC condition for 5d: Chiralpak IA column, hexanes:i-proh = 90:10, 1.0 ml/min, 220 nm, t minor = 3.8 min, t major = 5.0 min, ee = 98%. < HPLC chromatogram of racemic 5d > < HPLC chromatogram of chiral 5d > S26

27 Computational details All the calculations were conducted with Gaussian 09 software. 4 Geometry optimization of all species was carried out with the B3LYP functional. 5 The LANL2DZ basis set with ECP 6 was employed for Rh, and the 6-31G(d) basis set was used for the other atoms. Frequency analysis was performed to ensure the stationary point as minimum or transition state. For the solvent effect of dichloroethane, the single-point calculation on the optimized geometry with SMD solvation model. 7 The single-point calculation was carried out by using M06 8 with a mixed basis set (SDD 9 for Rh and G(d,p) for the other atoms). G(sol) kcal/mol E=CO 2 Me E=H A1-TS 20.1 N Cp* Rh O H O E B3-TS 17.4 N Rh Cp* E B1 0.0 A1 0.0 E N Rh Cp* O O B1-TS 19.2 B A E N Cp* Rh O HO N B3-4.9 A3-6.4 Rh Cp* E A3-TS 10.6 Cp* N Rh E B4-1.2 A B4-TS 1.5 A4-TS -5.1 H Cp* N Rh B5-6.4 E A5-7.3 Cp* N Rh H E C-H Activation Loss of Acetic Acid Migratory Insertion Reductive Elimination N H E A, E = CO 2 Me B, E = H Figure S1. Energy profiles of the proposed mechanism S27

28 Cartesian coordinates of optimized structures ( A ) A1 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H H C H H N Rh C C C C C O O C C H H H C H H C C S28

29 H H C O O C H H H C H H H C H H H C H H H C H H H C H H H A1-TS E(RM06) = Number of imaginary frequencies: 1 ( cm -1 ) C C C C C S29

30 C H H H H H C H H N Rh C C C C C O O C C H H H C H H C C H H C O O C H H H S30

31 C H H H C H H H C H H H C H H H C H H H A2 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H H C H H S31

32 N Rh C C C C C O O C C H H H C H H C C H H C O O C H H H C H H H C H H H C S32

33 H H H C H H H C H H H A3 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H C H H N Rh C C C C C C H H S33

34 C C H H C O O C H H H C H H H C H H H C H H H C H H H C H H H A3-TS E(RM06) = Number of imaginary frequencies: 1 ( cm -1 ) C C C S34

35 C C C H H H H C H H N Rh C C C C C C H H C C H H C O O C H H H C H H H C H S35

36 H H C H H H C H H H C H H H A4 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H C H H N Rh C C C C C S36

37 C H H C C H H C O O C H H H C H H H C H H H C H H H C H H H C H H H A4-TS E(RM06) = Number of imaginary frequencies: 1 ( cm -1 ) S37

38 C C C C C C H H H H C H H N Rh C C C C C C H H C C H H C O O C H H H C H H H C S38

39 H H H C H H H C H H H C H H H A5 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H C H H N Rh C C C C C S39

40 C H H C C H H C O O C H H H C H H H C H H H C H H H C H H H C H H H B1 E(RM06) = Number of imaginary frequencies: 0 C S40

41 C C C C C H H H H H C H H N Rh C C C C C O O C C H H H C H H C C H H C H H S41

42 H C H H H C H H H C H H H C H H H H B1-TS E(RM06) = Number of imaginary frequencies: 1 ( cm -1 ) C C C C C C H H H H H C H H N Rh S42

43 C C C C C O O C C H H H C H H C C H H C H H H C H H H C H H H C H H H C H S43

44 H H H B2 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H H H C H H N Rh C C C C C O O C C H H H C H H S44

45 C C H H C H H H C H H H C H H H C H H H C H H H H B3 E(RM06) = Number of imaginary frequencies: 0 C C C C C C H H H S45