Issue 17, 2018

Chiral proton-transfer shuttle catalysts for carbene insertion reactions

Abstract

Transition metal-catalyzed carbene insertion into X–H bonds (X = N, O, S, and C) represents a typical carbene transfer reaction and has been widely used in organic synthesis. The enantioselectivity-determining step in some of these insertion reactions is the proton transfer of active intermediates such as ylides, metal enolates, or free enols. Since most of the traditional chiral transition metal catalysts tend to dissociate from these active intermediates and cannot be involved in the proton-transfer step, enantiocontrol of these insertion reactions has long been a challenging task. Since 2011, we have developed chiral spiro phosphoric acids as chiral proton-transfer shuttle (CPTS) catalysts, which have been proven to be efficient catalysts for the proton transfer of active intermediates in carbene insertion reactions. Upon combining with achiral dirhodium catalysts, the CPTS catalysts accomplish highly enantioselective insertions of N–H, S–H, and C–H bonds. Herein, a number of important chiral building blocks, including α-amino acid derivatives, α-amino ketones, α-thioesters, and α,α-diaryl acetates, were prepared with high yields and high enantioselectivities through these insertion reactions.

Graphical abstract: Chiral proton-transfer shuttle catalysts for carbene insertion reactions

Article information

Article type
Review Article
Submitted
25 Feb 2018
Accepted
22 Mar 2018
First published
23 Mar 2018

Org. Biomol. Chem., 2018,16, 3087-3094

Chiral proton-transfer shuttle catalysts for carbene insertion reactions

Y. Ren, S. Zhu and Q. Zhou, Org. Biomol. Chem., 2018, 16, 3087 DOI: 10.1039/C8OB00473K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements