Access to Chiral Seven-Member Cyclic Amines via Rh-Catalyzed Asymmetric Hydrogenation

Pan Li; Yi Huang; Xinquan Hu; Xiu-Qin Dong; Xumu Zhang

doi:10.1021/acs.orglett.7b01726

Access to Chiral Seven-Member Cyclic Amines via Rh-Catalyzed Asymmetric Hydrogenation

Org Lett. 2017 Jul 21;19(14):3855-3858. doi: 10.1021/acs.orglett.7b01726. Epub 2017 Jul 3.

Authors

Pan Li^{1

2}, Yi Huang², Xinquan Hu¹, Xiu-Qin Dong², Xumu Zhang^{2

3}

Affiliations

¹ College of Chemical Engineering, Zhejiang University of Technology , Hangzhou, Zhejiang 310014, P. R. China.
² College of Chemistry and Molecular Sciences, Wuhan University , 430072, Wuhan, P. R. China.
³ Department of Chemistry, South University of Science and Technology of China , Shenzhen, 518000, P. R. China.

PMID: 28671474
DOI: 10.1021/acs.orglett.7b01726

Abstract

A highly efficient asymmetric hydrogenation of azepine/oxazepine-type seven-member cyclic imine hydrochlorides was successfully developed using Rh/bisphosphine-thiourea ligand ZhaoPhos, affording various chiral seven-member cyclic amines with full conversions, high yields, and excellent enantioselectivities (up to 96% yield, >99% ee). Additionally, this asymmetric hydrogenation can proceed well on gram scale with excellent ee value. Moreover, control experimental results displayed that the anion-bonding interaction between the chloride ion of the substrate and thiourea motif of the ZhaoPhos played an important role to obtain excellent enantioselectivity.

Publication types

Research Support, Non-U.S. Gov't