Palladium-Catalyzed Chemo- and Enantioselective C-O Bond Cleavage of α-Acyloxy Ketones by Hydrogenolysis

Jianzhong Chen; Zhenfeng Zhang; Delong Liu; Wanbin Zhang

doi:10.1002/anie.201603590

Palladium-Catalyzed Chemo- and Enantioselective C-O Bond Cleavage of α-Acyloxy Ketones by Hydrogenolysis

Angew Chem Int Ed Engl. 2016 Jul 11;55(29):8444-7. doi: 10.1002/anie.201603590. Epub 2016 Jun 17.

Authors

Jianzhong Chen¹, Zhenfeng Zhang², Delong Liu², Wanbin Zhang^{3

4}

Affiliations

¹ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P.R. China.
² School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P.R. China.
³ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P.R. China. wanbin@sjtu.edu.cn.
⁴ School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P.R. China. wanbin@sjtu.edu.cn.

PMID: 27312573
DOI: 10.1002/anie.201603590

Abstract

A chemoselective C-O bond cleavage of the ester alkyl side-chain of α-acyloxy ketones was realized for the first time by a highly efficient palladium-catalyzed hydrogenolysis (S/C=6000, the highest catalytic efficiency by far). Furthermore, a kinetic resolution of α-acyloxy ketones was first developed by enantioselective hydrogenolysis with good yields and up to 99 % ee.

Keywords: cleavage reactions; hydrogenolysis; ketones; kinetic resolution; palladium.

Publication types

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