Rh(III)-Catalyzed C-H Amidation with N-hydroxycarbamates: A. new Entry to N-Carbamate Protected Arylamines

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Rh(III)-Catalyzed C-H Amidation with N-hydroxycarbamates: A new Entry to N-Carbamate Protected Arylamines Bing Zhou,* Juanjuan Du, Yaxi Yang,* Huijin Feng, Yuanchao Li Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203, PR China zhoubing2012@hotmail.com; spyyx@163.com Table of contents: General Methods and Materials..1 X-ray structure of 3a 2 Experimental Procedures and Characterizations 2 1 H and 13 C NMR Spectra of Compounds..16 General methods: Mass spectra and high-resolution mass spectra were measured on a Finnigan MAT-95 mass spectrometer. 1 H and 13 C NMR spectra were determined on Bruker AM-300, Bruker AM-400, Bruker AM-500 instruments using tetramethylsilane as internal reference. Data are presented as follows: chemical shift, multiplicity (s = singlet, br s = broad singlet, d = doublet, br d = broad doublet, t = triplet, m = multiplet), J = coupling constant in hertz (Hz). Silica gel 60H (200-300 mesh) manufactured by Qingdao Haiyang Chemical Group Co. (China) was used for general chromatography. Materials: 2-Phenylpyridine, tert-butyl N-hydroxy carbamate, Benzyl N-hydroxy carbamate, Acetohydroxamic acid and silver carbonate was purchased from Adamas-beta and used without further purification. [Cp*RhCl 2 ] 2 S1, [Cp*Rh(MeCN) 3 ][SbF 6 ] 2 S2 and other hydroxycarbamates S3 were synthesized according to published procedures. 1

X-ray structure of 3a Experimental Procedures and Characterizations: [Cp*Rh(MeCN) 3 ][SbF 6 ] 2 (2.5mol%), 2-Phenylpyridine (1) (0.2mmol), Benzyl N-hydroxy carbamate (2a) (0.24 mmol), Ag 2 CO 3 (0.3 mmol), THF (1 ml) were added in a sealed tube. It was stirred at 100 for 10h. The volatile was removed under reduced pressure and the crude product was purified by column chromatography on silica gel. benzyl 2-(pyridin-2-yl)phenylcarbamate(3a) chromatography on silica gel in 77% yield. 2

1 H NMR (300 MHz, CDCl 3 ) δ 11.52 (s, 1H), 8.68 8.61 (m, 1H), 8.34 (d, J = 8.3 Hz, 1H), 7.82 (m, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.62 (dd, J = 7.9, 1.4 Hz, 1H), 7.45 7.29 (m, 6H), 7.28 7.23 (m, 1H), 7.13 (m, 1H), 5.21 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 158.2, 153.9, 147.7, 137.7, 137.6, 136.6, 130.1, 129.0, 128.5, 128.2, 128.1, 122.9, 122.7, 121.8, 120.6, 66.6. HRMS (EI) calcd. for C 19 H 16 N 2 O 2 [M]+ : 304.1212. Found: 304.1205. benzyl 5-methyl-2-(pyridin-2-yl)phenylcarbamate(3b) chromatography on silica gel in 70% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 11.70 (s, 1H), 8.61 (d, J = 4.1 Hz, 1H), 8.20 (s, 1H), 7.82 7.74 (m, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.38 (m, 5H), 7.21 (m, 1H), 6.94 (d, J = 8.0 Hz, 1H), 5.21 (s, 2H), 2.41 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 158.3, 154.0, 147.6, 140.4, 137.7, 137.5, 136.7, 128.7, 128.5, 128.1, 128.1, 123.6, 122.6, 122.5, 121.4, 120.9, 66.5, 21.7. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1371. benzyl 5-methoxy-2-(pyridin-2-yl)phenylcarbamate(3c) chromatography on silica gel in 80% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 12.11 (s, 1H), 8.59 (d, J = 5.6 Hz, 1H), 8.05 (s, 1H), 7.76 (t, J = 7.8 Hz, 1H), 7.65 (d, J = 7.7 Hz, 1H), 7.58 (d, J = 8.8 Hz, 1H), 7.46 7.29 3

(m, 5H), 7.22 7.12 (m, 1H), 6.67 (dd, J = 8.8, 1.9 Hz, 1H), 5.22 (s, 2H), 3.88 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 161.0, 158.1, 154.0, 147.4, 139.6, 137.5, 136.6, 129.8, 128.5, 128.1, 128.1, 121.9, 121.0, 117.5, 109.6, 104.4, 66.5, 55.4. HRMS (EI) calcd. for C 20 H 18 N 2 O 3 [M]+ : 334.1317. Found: 334.1313. methyl 3-(benzyloxycarbonylamino)-4-(pyridin-2-yl)benzoate(3d) chromatography on silica gel in 92% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.63 (s, 1H), 9.02 (s, 1H), 8.69 (d, J = 4.9 Hz, 1H), 7.87 (td, J = 7.9, 1.8 Hz, 1H), 7.82 (dd, J = 8.2, 1.7 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.72 (d, J = 8.2 Hz, 1H), 7.45 (d, J = 7.2 Hz, 2H), 7.36 (m, 4H), 5.25 (s, 2H), 3.96 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 166.7, 157.2, 153.8, 147.9, 137.9, 137.8, 136.5, 131.4, 128.9, 128.5, 128.2, 128.2, 123.7, 123.3, 122.5, 121.6, 66.7, 52.3. HRMS (EI) calcd. for C 21 H 18 N 2 O 4 [M]+ : 362.1267. Found: 362.1262. benzyl 5-chloro-2-(pyridin-2-yl)phenylcarbamate(3e) chromatography on silica gel in 70% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 11.83 (s, 1H), 8.63 (d, J = 4.3 Hz, 1H), 8.46 (s, 1H), 7.81 (t, J = 7.5 Hz, 1H), 7.67 (d, J = 8.1 Hz, 1H), 7.55 (d, J = 8.5 Hz, 1H), 7.47 7.21 (m, 5H), 7.26 (t, J = 5.9 Hz, 1H), 7.08 (d, J = 8.5 Hz, 1H), 5.22 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 157.3, 153.7, 147.7, 139.0, 137.8, 136.4, 136.0, 129.8, 128.6, 4

128.3, 128.2, 123.3, 122.7, 122.6, 122.0, 120.2, 66.8. HRMS (EI) calcd. for C 19 H 15 ClN 2 O 2 [M]+ : 338.0822. Found: 338.0828. benzyl 5-bromo-2-(pyridin-2-yl)phenylcarbamate(3f) chromatography on silica gel in 70% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 11.81 (s, 1H), 8.62 (d, J = 6.0 Hz, 2H), 7.81 (t, J = 7.8 Hz, 1H), 7.67 (d, J = 8.1 Hz, 1H), 7.40 (m, 6H), 7.29 7.19 (m, 2H), 5.22 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 157.3, 153.7, 147.7, 139.0, 137.8, 136.4, 130.0, 128.6, 128.3, 128.2, 125.6, 124.2, 123.7, 123.1, 122.6, 122.1, 66.8. HRMS (EI) calcd. for C 19 H 15 BrN 2 O 2 [M]+ : 382.0317. Found: 382.0319. benzyl 4-methyl-2-(pyridin-2-yl)phenylcarbamate(3g) chromatography on silica gel in 64% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.29 (s, 1H), 8.69 8.63 (m, 1H), 8.22 (d, J = 8.3 Hz, 1H), 7.82 (td, J = 7.8, 1.9 Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.47 7.32 (m, 6H), 7.28 7.22 (m, 2H), 5.22 (s, 2H), 2.39 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 158.2, 154.0, 147.7, 137.5, 136.7, 135.0, 132.1, 130.6, 129.4, 128.5, 128.2, 128.0, 122.9, 121.7, 120.7, 66.5, 20.8. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1376. 5

benzyl 4-methoxy-2-(pyridin-2-yl)phenylcarbamate(3h) chromatography on silica gel in 60% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.05 (s, 1H), 8.67 (d, J = 4.9 Hz, 1H), 8.22 (d, J = 8.8 Hz, 1H), 7.84 (td, J = 7.9, 1.8 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.45 7.31 (m, 5H), 7.28 (m, 1H), 7.16 (d, J = 2.9 Hz, 1H), 7.00 (dd, J = 9.1, 2.9 Hz, 1H), 5.20 (s, 2H), 3.87 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 159.4, 156.5, 155.5, 149.3, 139.0, 138.2, 132.3, 129.9, 129.6, 129.4, 124.4, 123.4, 116.3, 116.2, 67.9, 57.1. HRMS (EI) calcd. for C 20 H 18 N 2 O 3 [M]+ : 334.1317. Found: 334.1314. benzyl 4-chloro-2-(pyridin-2-yl)phenylcarbamate(3i) chromatography on silica gel in 54% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.50 (s, 1H), 8.68 (d, J = 4.3 Hz, 1H), 8.33 (d, J = 8.8 Hz, 1H), 7.86 (td, J = 7.8, 1.8 Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.61 (d, J = 2.5 Hz, 1H), 7.46 7.34 (m, 6H), 7.31 (ddd, J = 7.5, 4.9, 0.9 Hz, 1H), 5.22 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.9, 153.8, 147.9, 137.9, 136.5, 136.4, 129.8, 128.6, 128.5, 128.2, 128.2, 127.7, 122.9, 122.4, 122.0, 66.7. HRMS (EI) calcd. for C 19 H 15 ClN 2 O 2 [M]+ : 338.0822. Found: 338.0816. 6

benzyl 3-methyl-2-(pyridin-2-yl)phenylcarbamate(3j) chromatography on silica gel in 65% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 8.76 (d, J = 4.3 Hz, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.85 7.72 (m, 2H), 7.38 7.29 (m, 8H), 7.05 (d, J = 7.6 Hz, 1H), 5.13 (s, 2H), 2.18 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.7, 153.6, 149.8, 136.9, 136.3, 136.2, 135.6, 128.9, 128.5, 128.2, 128.2, 126.2, 125.8, 122.4, 66.7, 20.8. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1372. benzyl 2-(pyridin-2-yl)thiophen-3-ylcarbamate(3k) chromatography on silica gel in 65% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 11.62 (s, 1H), 8.55 8.50 (m, 1H), 7.97 (s, 1H), 7.70 7.62 (m, 1H), 7.48 7.31 (m, 6H), 7.27 7.22 (m, 1H), 7.11 7.03 (m, 1H), 5.25 (s, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 154.1, 153.6, 147.9, 138.5, 137.0, 136.4, 128.5, 128.2, 128.2, 124.6, 122.9, 120.3, 120.1, 118.3, 66.8. HRMS (EI) calcd. for C 17 H 14 N 2 O 2 S [M]+ : 310.0776. Found: 310.0774. benzyl 2-(3-methylpyridin-2-yl)phenylcarbamate(3l) chromatography on silica gel in 55% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 8.54 (d, J = 3.8 Hz, 1H), 8.23 (d, J = 22.1 Hz, 2H), 7.68 (d, J = 7.7 Hz, 1H), 7.44 7.32 (m, 6H), 7.25 (m, 2H), 7.15 (td, J = 7.5, 1.0 Hz, 7

1H), 5.16 (s, 2H), 2.30 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 156.3, 153.5, 146.6, 139.6, 136.2, 135.6, 132.4, 129.9, 129.1, 128.4, 128.2, 128.1, 122.7, 122.5, 66.7, 19.8. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1375. benzyl 2-(4-methylpyridin-2-yl)phenylcarbamate(3m) chromatography on silica gel in 50% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.53 (s, 1H), 8.52 (d, J = 5.1 Hz, 1H), 8.34 (d, J = 8.3 Hz, 1H), 7.63 (dd, J = 7.9, 1.4 Hz, 1H), 7.54 (s, 1H), 7.47 7.32 (m, 6H), 7.13 (m, 2H), 5.23 (s, 2H), 2.45 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 157.9, 153.9, 148.8, 147.5, 137.7, 136.6, 129.8, 128.8, 128.4, 128.1, 128.0, 123.7, 122.9, 122.6, 120.5, 66.5, 21.4. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1373. benzyl 2-(5-methylpyridin-2-yl)phenylcarbamate(3n) chromatography on silica gel in 60% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.46 (s, 1H), 8.50 (s, 1H), 8.33 (d, J = 8.2 Hz, 1H), 7.63 (m, 3H), 7.48 7.32 (m, 6H), 7.16 7.09 (m, 1H), 5.23 (s, 2H), 2.40 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 155.3, 153.9, 148.0, 138.3, 137.4, 136.6, 131.5, 129.7, 128.7, 128.4, 128.2, 128.0, 122.7, 122.4, 120.6, 66.5, 18.1. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1360. 8

benzyl 2-(6-methylpyridin-2-yl)phenylcarbamate(3o) chromatography on silica gel in 50% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 12.19 (s, 1H), 8.37 (d, J = 8.3 Hz, 1H), 7.72 (t, J = 7.8 Hz, 1H), 7.68 (dd, J = 7.9, 1.5 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.46 7.34 (m, 6H), 7.13 (m, 2H), 5.25 (s, 2H), 2.63 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 158.9, 157.8, 155.3, 139.4, 139.2, 138.2, 131.3, 130.0, 129.8, 129.3, 129.1, 123.8, 122.6, 121.5, 121.0, 67.7, 25.7. HRMS (EI) calcd. for C 20 H 18 N 2 O 2 [M]+ : 318.1368. Found: 318.1365. benzyl 2-(5-chloropyridin-2-yl)phenylcarbamate(3p) chromatography on silica gel in 56% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.10 (s, 1H), 8.63 (d, J = 2.1 Hz, 1H), 8.35 (d, J = 8.3 Hz, 1H), 7.81 (dd, J = 8.6, 2.5 Hz, 1H), 7.68 (d, J = 8.6 Hz, 1H), 7.59 (dd, J = 7.9, 1.4 Hz, 1H), 7.46 7.33 (m, 6H), 7.18 7.12 (m, 1H), 5.22 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.2, 153.8, 146.6, 137.5, 137.4, 136.4, 130.4, 130.3, 128.9, 128.5, 128.3, 128.1, 123.7, 122.8, 120.7, 66.6. HRMS (EI) calcd. for C 19 H 15 ClN 2 O 2 [M]+ : 338.0822. Found: 338.0816. 9

benzyl benzo[h]quinolin-10-ylcarbamate(3q) chromatography on silica gel in 53% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 8.96 (dd, J = 4.5, 1.8 Hz, 1H), 8.84 (d, J = 8.1 Hz, 1H), 8.24 (dd, J = 8.0, 1.8 Hz, 1H), 7.82 (d, J = 8.8 Hz, 1H), 7.72 (t, J = 7.9 Hz, 1H), 7.66 (d, J = 8.8 Hz, 1H), 7.60 (d, J = 7.8 Hz, 1H), 7.55 (dd, J = 7.9, 4.6 Hz, 3H), 7.43 (t, J = 7.4 Hz, 2H), 7.39 7.34 (m, 1H), 5.36 (s, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 154.4, 147.8, 145.9, 139.5, 136.9, 136.3, 135.0, 129.2, 128.8, 128.5, 128.0, 127.9, 127.3, 125.1, 122.0, 120.6, 117.3, 116.6, 66.3. HRMS (EI) calcd. for C 21 H 16 N 2 O 2 [M]+ : 328.1212. Found: 328.1205. benzyl 2-(pyrimidin-2-yl)phenylcarbamate(3r) chromatography on silica gel in 60% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 12.11 (s, 1H), 8.85 (d, J = 4.9 Hz, 2H), 8.58 (dd, J = 8.1, 1.7 Hz, 1H), 8.48 (d, J = 8.3 Hz, 1H), 7.53 7.45 (m, 3H), 7.44 7.34 (m, 3H), 7.22 (t, J = 4.9 Hz, 1H), 7.19 7.14 (m, 1H), 5.27 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 165.0, 156.4, 153.8, 139.8, 136.6, 132.0, 130.6, 128.5, 128.2, 128.1, 122.4, 122.2, 119.6, 118.3, 66.6. HRMS (EI) calcd. for C 18 H 15 N 3 O 2 [M]+ : 305.1164. Found: 305.1169. benzyl 3-methyl-2-(pyrimidin-2-yl)phenylcarbamate(3s) chromatography on silica gel in 64% yield. 10

1 H NMR (400 MHz, CDCl 3 ) δ 8.91 (d, J = 4.9 Hz, 1H), 8.85 (s, 1H), 7.99 (s, 1H), 7.38 (m, 4H), 7.34 (m, 2H), 7.30 7.27 (m, 1H), 7.07 (d, J = 7.5 Hz, 1H), 5.15 (s, 2H), 2.35 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 165.6, 156.9, 153.5, 137.9, 136.2, 136.0, 129.6, 128.4, 128.2, 128.1, 126.3, 118.8, 66.7, 21.3. HRMS (EI) calcd. For C 19 H 17 N 3 O 2 [M]+ : 319.1321. Found: 319.1323. benzyl 2-(1H-pyrazol-1-yl)phenylcarbamate(3t) chromatography on silica gel in 46% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 9.66 (s, 1H), 8.34 (d, J = 8.0 Hz, 1H), 7.81 (dd, J = 5.5, 2.1 Hz, 2H), 7.45 7.34 (m, 6H), 7.31 (dd, J = 8.0, 1.4 Hz, 1H), 7.14 (td, J = 7.9, 1.4 Hz, 1H), 6.50 (t, J = 2.2 Hz, 1H), 5.21 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 153.5, 141.3, 136.2, 131.9, 130.0, 128.5, 128.3, 128.2, 128.1, 123.1, 122.6, 121.3, 107.1, 66.9. HRMS (EI) calcd. For C 17 H 15 N 3 O 2 [M]+ : 293.1164. Found: 293.1168. (E)-benzyl 2-(1-(methoxyimino)ethyl)phenylcarbamate(3u) chromatography on silica gel in 55% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 10.64 (s, 1H), 8.33 (d, J = 8.3 Hz, 1H), 7.46 7.35 (m, 7H), 7.12 7.06 (m, 1H), 5.25 (s, 2H), 4.04 (s, 3H), 2.31 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 156.3, 153.7, 136.9, 136.5, 129.7, 128.4, 128.3, 128.0, 127.8, 122.3, 122.2, 119.6, 66.4, 62.2, 13.6. HRMS (EI) calcd. For C 17 H 18 N 2 O 3 [M]+ : 298.1317. Found: 298.1325. 11

(E)-benzyl 2-(1-(methoxyimino)ethyl)-5-methylphenylcarbamate(3v) chromatography on silica gel in 60% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 10.69 (s, 1H), 8.15 (s, 1H), 7.36 (m, 6H), 6.87 (d, J = 8.1 Hz, 1H), 5.22 (s, 2H), 4.00 (s, 3H), 2.36 (s, 3H), 2.26 (s, 3H). 13 C NMR (151 MHz, CDCl 3 ) δ 156.4, 153.8, 140.1, 136.9, 136.7, 128.5, 128.3, 128.0, 127.8, 123.1, 120.1, 119.6, 66.4, 62.2, 21.6, 13.5. HRMS (EI) calcd. For C 18 H 20 N 2 O 3 [M]+ : 312.1474. Found: 312.1477. (E)-benzyl 5-bromo-2-(1-(methoxyimino)ethyl)phenylcarbamate(3w) chromatography on silica gel in 44% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 10.80 (s, 1H), 8.57 (d, J = 1.8 Hz, 1H), 7.36 (m, 6H), 7.17 (dd, J = 8.5, 2.0 Hz, 1H), 5.22 (s, 2H), 4.01 (s, 3H), 2.25 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 155.9, 153.5, 138.3, 136.3, 129.5, 128.5, 128.1, 127.8, 125.2, 123.9, 122.2, 120.7, 66.7, 62.4, 13.5. HRMS (EI) calcd. for C 17 H 17 BrN 2 O 3 [M]+ : 376.0423. Found: 376.0419. 4-methoxybenzyl 2-(pyridin-2-yl)phenylcarbamate(3x) 12

chromatography on silica gel in 70% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.48 (s, 1H), 8.66 (d, J = 3.9 Hz, 1H), 8.36 (d, J = 8.1 Hz, 1H), 7.83 (td, J = 7.8, 1.9 Hz, 1H), 7.72 (d, J = 8.2 Hz, 1H), 7.63 (dd, J = 7.9, 1.2 Hz, 1H), 7.46 7.36 (m, 3H), 7.28 7.24 (m, 1H), 7.14 (t, J = 7.1 Hz, 1H), 6.92 (d, J = 8.6 Hz, 2H), 5.16 (s, 2H), 3.83 (s, 3H). 13 C NMR (101 MHz, cdcl 3 ) δ 159.4, 158.1, 153.9, 147.7, 137.6, 137.5, 130.0, 129.9, 128.9, 128.6, 122.9, 122.6, 121.7, 120.5, 113.8, 66.3, 55.2. HRMS (EI) calcd. For C 20 H 18 N 2 O 3 [M]+ : 334.1317. Found: 334.1322. N-(2-(pyridin-2-yl)phenyl)acetamide(3y) chromatography on silica gel in 68% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 12.11 (s, 1H), 8.67 (d, J = 4.1 Hz, 1H), 8.54 (d, J = 8.1 Hz, 1H), 7.87 (td, J = 7.8, 1.8 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.66 (dd, J = 7.9, 1.4 Hz, 1H), 7.47 7.40 (m, 1H), 7.31 (dd, J = 7.0, 5.4 Hz, 1H), 7.19 (t, J = 7.1 Hz, 1H), 2.20 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 168.6, 158.3, 147.4, 137.7, 137.5, 130.0, 128.8, 125.6, 123.5, 123.1, 121.9, 121.9, 25.2. HRMS (EI) calcd. For C 13 H 12 N 2 O[M]+ : 212.0950. Found: 212.0947. tert-butyl 2-(pyridin-2-yl)phenylcarbamate(3z) chromatography on silica gel in 60% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.10 (s, 1H), 8.68 (d, J = 4.0 Hz, 1H), 8.33 (d, J = 8.2 Hz, 1H), 7.87 7.80 (m, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.61 (dd, J = 7.8, 1.5 Hz, 1H), 13

7.43 7.36 (m, 1H), 7.31 7.26 (m, 1H), 7.11 (td, J = 7.8, 1.2 Hz, 1H), 1.54 (s, 9H). 13 C NMR (126 MHz, CDCl 3 ) δ 159.8, 154.8, 149.1, 139.5, 138.9, 131.3, 130.4, 126.9, 124.4, 123.6, 123.0, 121.8, 81.2, 29.8. HRMS (EI) calcd. For C 16 H 18 N 2 O 2 [M]+ : 270.1368. Found: 270.1360. (9H-fluoren-9-yl)methyl 2-(pyridin-2-yl)phenylcarbamate(3aa) chromatography on silica gel in 55% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 11.91 (s, 1H), 8.76 (d, J = 4.2 Hz, 1H), 8.32 (s, 1H), 7.89 (td, J = 7.9, 1.8 Hz, 1H), 7.80 (dd, J = 7.8, 3.3 Hz, 3H), 7.74 7.64 (m, 3H), 7.44 (m, 3H), 7.38 7.30 (m, 3H), 7.21 7.15 (m, 1H), 4.45 (d, J = 7.6 Hz, 2H), 4.35 (t, J = 7.5 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ 158.2, 153.8, 147.4, 143.9, 141.3, 137.7, 137.6, 130.1, 128.7, 127.6, 127.0, 125.2, 122.9, 122.7, 121.8, 120.6, 119.9, 66.8, 47.0. HRMS (EI) calcd. For C 26 H 20 N 2 O 2 [M]+ : 392.1525. Found:392.1532. Mechanistic study: [Cp*Rh(MeCN) 3 ][SbF 6 ] 2 (2.5mol%), 2-Phenylpyridine (1) (0.1mmol) and D5-1 (0.1mmol), Acetohydroxamic acid (0.24mmol), silver carbonate (0.3mmol), THF (1ml) were added in a round-bottom flask. It was stirred at 100 for 2h, then 14

immediately quenched with EtOAc at the same time. The volatile was removed under reduced pressure and the crude product was purified by column chromatography on silica gel. Reference: S1: K. Fujita, Y. Takahashi, M. Owaki, K. Yamamoto, R. Yamaguchi, Org. Lett. 2004, 6, 2785. S2: Yang Li, Bi-Jie Li, Wen-Hua Wang, Wei-Ping Huang, Xi-Sha Zhang, Kang Chen, and Zhang-Jie Shi, Angew. Chem. Int. Ed. 2011, 50, 2115. S3: Donohoe, T.J., Chughtai, M.J., Klauber, D. J., Griffin, D., Cambell, A. D., J. Am. Chem. Soc. 2006, 128, 2514. 15

1 H and 13 C NMR Spectra of Compounds Compound 3a 16

Compound 3b 17

Compound 3c 18

Compound 3d 19

Compound 3e 20

Compound 3f 21

Compound 3g 22

Compound 3h 23

Compound 3i 24

Compound 3j 25

Compound 3k 26

Compound 3l 27

Compound 3m 28

Compound 3n 29

Compound 3o 30

Compound 3p 31

Compound 3q 32

Compound 3r 33

Compound 3s 34

Compound 3t 35

Compound 3u 36

Compound 3v 37

Compound 3w 38

Compound 3x 39

Compound 3y 40

Compound 3z 41

Compound 3aa 42

KIE experiment: 43

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