Synthesis 2008(4): 655-659  
DOI: 10.1055/s-2007-990885
PSP
© Georg Thieme Verlag Stuttgart · New York

A Convenient, High-Yielding Copper-Free Synthesis of Skipped 1,4-Diynes

Jilali Kessabi, Renaud Beaudegnies, Pierre M. J. Jung, Benjamin Martin, Florian Montel, Sebastian Wendeborn*
Research Chemistry, SYNGENTA Crop Protection AG, 4002 Basel, Switzerland
Fax: +41(61)3238529; e-Mail: [email protected];
Further Information

Publication History

Received 14 August 2007
Publication Date:
13 November 2007 (online)

Abstract

Alkynylalanes were found to react efficiently with propargylic electrophiles, such as propargyl mesylates and propargyl diethylphosphates. The reaction proceeds with high regioselectivity and does not require copper or any other transition metal.

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9

The need for two equivalents of alkynylalane when employing propargyl phosphates and phosphinates suggests that the reaction proceeds via an alternative mechanism, essentially involving Lewis acid activation prior to coordination and transfer brought on by the second equivalent of alkynylalane.

11

Unpublished results from this laboratory.