Pentanidium-Catalyzed Direct Assembly of Vicinal All-Carbon Quaternary Stereocenters through C(sp³)–C(sp³) Bond Formation

Authors

Xu Ban, Henan University
Yifan Fan, Henan University
Tuan Khoa Kha, Nanyang Technological University
Richmond Lee, University of Wollongong
Choon Wee Kee, Nanyang Technological University
Zhiyong Jiang, Henan University
Choon Hong Tan, Nanyang Technological University

Publication Name

CCS Chemistry

Abstract

The stereoselective construction of vicinal all-carbon quaternary stereocenters has long been a formidable synthetic challenge. Direct asymmetric coupling of a tertiary carbon nucleophile with a tertiary carbon electrophile is the most straightforward approach, but it is sterically and energetically disfavored. Herein, we describe a catalytic asymmetric substitution, where racemic tertiary bromides coupled directly with racemic secondary or tertiary carbanion, creating a series of congested C(sp3)–C(sp3) bonds, including isolated all-carbon quaternary stereocenters, vicinal tertiary/all-carbon quaternary stereocenters and vicinal all-carbon quaternary stereocenters. Using pentanidium as a catalyst, this double stereoconvergent process afforded substituted products in good enantioselectivities and diastereoselectivities.

Open Access Status

This publication may be available as open access

Volume

3

Issue

10

First Page

2192

Last Page

2200

Funding Number

DECRA DE210100053

Funding Sponsor

Australian Research Council