Bimetallic Gold(I)/Chiral N,N'-Dioxide Nickel(II) Asymmetric Relay Catalysis: Chemo- and Enantioselective Synthesis of Spiroketals and Spiroaminals

Jun Li; Lili Lin; Bowen Hu; Xiangjin Lian; Gang Wang; Xiaohua Liu; Xiaoming Feng

doi:10.1002/anie.201601701

Bimetallic Gold(I)/Chiral N,N'-Dioxide Nickel(II) Asymmetric Relay Catalysis: Chemo- and Enantioselective Synthesis of Spiroketals and Spiroaminals

Angew Chem Int Ed Engl. 2016 May 10;55(20):6075-8. doi: 10.1002/anie.201601701. Epub 2016 Apr 8.

Authors

Jun Li¹, Lili Lin¹, Bowen Hu¹, Xiangjin Lian¹, Gang Wang¹, Xiaohua Liu², Xiaoming Feng^{3

4}

Affiliations

¹ Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.
² Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China. liuxh@scu.edu.cn.
³ Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China. xmfeng@scu.edu.cn.
⁴ Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China. xmfeng@scu.edu.cn.

PMID: 27062196
DOI: 10.1002/anie.201601701

Abstract

A highly efficient asymmetric cascade reaction between keto esters and alkynyl alcohols and amides is reported. The success of the reaction was attributed to the combination of chiral Lewis acid N,N'-dioxide nickel(II) catalysis with achiral π-acid gold(I) catalysis working as an asymmetric relay catalytic system. The corresponding spiroketals and spiroaminals were synthesized in up to 99 % yield, 19:1 d.r., and more than 99 % ee under mild reaction conditions. Control experiments suggest that the N,N'-dioxide ligand was essential for the formation of the spiro products.

Keywords: asymmetric catalysis; cascade reactions; gold; nickel; relay catalysis.

Publication types

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