Issue 7, 2017

Enantioselective palladium-catalyzed diboration of 1,1-disubstituted allenes

Abstract

A practical and enantioselective palladium-catalyzed diboration of 1,1-disubstituted allenes is developed by employing a P-chiral monophosphorus ligand, BI-DIME. A series of diboronic esters containing a chiral tertiary boronic ester moiety are formed in excellent yields and ee’s with the palladium loading as low as 0.2 mol%. DFT calculations revealed a concerted mechanism of oxidative addition of bis(pinacolato)diboron and allene insertion, as well as a critical dispersion effect on the origins of the enantioselectivity. The method is successfully applied to the concise and enantioselective synthesis of brassinazole.

Graphical abstract: Enantioselective palladium-catalyzed diboration of 1,1-disubstituted allenes

Supplementary files

Article information

Article type
Edge Article
Submitted
20 Mar 2017
Accepted
07 May 2017
First published
16 May 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 5161-5165

Enantioselective palladium-catalyzed diboration of 1,1-disubstituted allenes

J. Liu, M. Nie, Q. Zhou, S. Gao, W. Jiang, L. W. Chung, W. Tang and K. Ding, Chem. Sci., 2017, 8, 5161 DOI: 10.1039/C7SC01254C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements