Synlett 2015; 26(19): 2702-2706
DOI: 10.1055/s-0035-1560265
letter
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of Trisubstituted Vinyl Bromides by Addition of Alkynes to Oxocarbenium Ions

Andrew R. Ehle
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA   Email: mpwatson@udel.edu
,
Melissa G. Morris
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA   Email: mpwatson@udel.edu
,
Bryan D. Klebon
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA   Email: mpwatson@udel.edu
,
Glenn P. A. Yap
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA   Email: mpwatson@udel.edu
,
Mary P. Watson*
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA   Email: mpwatson@udel.edu
› Author Affiliations
Further Information

Publication History

Received: 07 July 2015

Accepted after revision: 20 August 2015

Publication Date:
14 September 2015 (online)

Abstract

We have developed an efficient method for the synthesis of trisubstituted (E)-vinyl bromides by a Friedel–Crafts-type addition of alkynes to oxocarbenium ions formed in situ from acetals. The success of this reaction relies on the identification of magnesium bromide etherate as both a Lewis-acid promoter and a source of bromide. This reaction employs simple inexpensive starting materials and proceeds under mild conditions to allow the preparation of a range of vinyl bromide products in high yields and high E/Z selectivities. Furthermore, the vinyl bromides also contain an allylic ether functional group. Both the vinyl bromide and allylic ether groups are effective handles for the elaboration of these useful synthetic intermediates.

Supporting Information

 
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