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. 2011 Aug 19;13(16):4172-5.
doi: 10.1021/ol2014736. Epub 2011 Jul 25.

Transition-metal-free alkynylation of aryl chlorides

Thanh Truong  1 , Olafs Daugulis
Affiliations

Transition-metal-free alkynylation of aryl chlorides

Thanh Truong et al. Org Lett. .

Abstract

Two sets of conditions have been developed for a base-mediated, transition-metal-free alkynylation of aryl chlorides that proceeds via benzyne intermediates. The first set of conditions involves the use of TMPLi base in a pentane/THF mixture at 25 °C. The second set involves use of a metal alkoxide base in dioxane at elevated temperature. Reasonable functional group tolerance has been observed. Fluoro, trifluoromethyl, silyl, cyano, and alcohol functionalities are compatible with the reaction conditions.

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Figures

Scheme 1
Scheme 1
Deuteration Experiments
Scheme 2
Scheme 2
Metalation-Benzyne Formation Sequence
See this image and copyright information in PMC

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