N-(4-methylphenyl)-3-exo-(4-methoxybenzyl)tricyclo[3.2.1.02,4]octane-6,7-end o-dicarboximide

N-(4-methylphenyl)-3-exo-(4-methoxybenzyl)tricyclo[3.2.1.02,4]octane-6,7-end o-dicarboximide

petroleum ether/EtOAc (10/1→3/1) to give white solid, 185.8 mg, 96 % yield. Mp: 193-195 oC; 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.0 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 3.81 (s, 3H), 3.21 (s, 2H), 2.99 (s, 2H), 2.46 (d, J = 6.4 Hz, 2H), 2.40 (s, 3H), 1.40 (d, J = 11.2 Hz, 1H), 1.22 (t, J = 6.4 Hz, 1H), 1.07 (d, J = 10.8 Hz, 1H), 0.92 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 177.2, 157.9, 138.7, 132.3, 129.8, 129.4, 129.2, 126.4, 113.6, 55.1, 49.3, 39.0, 35.8, 31.7, 21.2, 17.9, 14.0; HRMS (EI) calcd. for C25H25NO3 [M+ ]: 387.1834, found: 387.1840

Palladium(0)-Catalyzed Methylcyclopropanation of Norbornenes with Vinyl Bromides and Mechanism Study Jiangang Mao, †,‡ Hujun Xie,§Weiliang Bao*,† †Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, P. R. China ‡School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, 86 Hongqi Avenue, Ganzhou 341000, Jiangxi, P. R. China §School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou, 310035 Zhejiang, P.R. China E-mail: wlbao@zju.edu.cn

Palladium(0)-Catalyzed Methylcyclopropanation of Norbornenes with Vinyl Bromides and Mechanism Study

Jiangang Mao†‡, Hujun Xie§, and Weiliang Bao*†

† Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, P.R. China

‡ School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, P.R. China

§ School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035, Zhejiang P.R. China

Org. Lett., 2015, 17 (15), pp 3678–3681

DOI: 10.1021/acs.orglett.5b01603

*E-mail: wlbao@zju.edu.cn.

Abstract

An unusual methylcyclopropanation from [2 + 1] cycloadditions of vinyl bromides to norbornenes catalyzed by Pd(OAc)2/PPh3 in the presence of CH3ONa and CH3OH has been established. A methylcyclopropane subunit was installed by a 3-fold domino procedure involving a key protonation course. Preliminary deuterium-labeling studies revealed that the proton came from methyl of CH3OH and also exposed an additional hydrogen/deuterium exchange process. These two proton-concerned reactions were fully chemoselective.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.5b01603

J. Mao, H. Xie, W. Bao, Org. Lett. 2015, 17, 3678 – 3681

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