Issue 19, 2019

Brønsted acid and Pd–PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes

Abstract

We describe the development of Pd–PHOX-catalysed enantioselective couplings of internal dienes with malononitrile and other activated C-pronucleophiles. Reactions are dramatically accelerated by the addition of Et3N·HBArF4 as a Brønsted acid co-catalyst, enabling a suite of products bearing a variety of alkyl substituents at the stereogenic carbon to be prepared. A series of mechanism-oriented experiments reveal key aspects of the catalytic cycle and the importance of the non-coordinating BArF4 counterion in not only promoting reactions of internal dienes but also additions of previously unreactive nucleophiles towards terminal dienes.

Graphical abstract: Brønsted acid and Pd–PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes

Supplementary files

Article information

Article type
Edge Article
Submitted
04 Feb 2019
Accepted
16 Apr 2019
First published
17 Apr 2019
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., 2019,10, 5176-5182

Brønsted acid and Pd–PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes

S. Park, N. J. Adamson and S. J. Malcolmson, Chem. Sci., 2019, 10, 5176 DOI: 10.1039/C9SC00633H

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.

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