A non-traditional approach to synthesizing aryl vinyl sulfides is described. 2,2-diphenyl-1,3-oxathiolane slowly liberates vinyl sulfide anion under basic conditions. Using a Pd/Xantphos catalyst system to activate a wide range of aryl bromides, this transient sulfide species can be effectively trapped and fed into a traditional Pd0/PdII catalytic cycle. Scope and limitations of the methodology are presented along with significant discussion of a competitive C–S bond activation by this catalyst system.

Authors

Jason R. Schmink, Bryn Mawr CollegeFollow
Summer A. Baker Dockrey
Tianyi Zhang
Naomi Chebet
Alexis van Venrooy
Mary Sexton
Sarah I. Lew
Steffany Chou
Ami Okazaki

Document Type

Article

Version

Author's Final Manuscript

Publication Title

Organic Letters

Volume

18

Publication Date

12-2016

Abstract

A non-traditional approach to synthesizing aryl vinyl sulfides is described. 2,2-diphenyl-1,3-oxathiolane slowly liberates vinyl sulfide anion under basic conditions. Using a Pd/Xantphos catalyst system to activate a wide range of aryl bromides, this transient sulfide species can be effectively trapped and fed into a traditional Pd⁰/Pd^II catalytic cycle. Scope and limitations of the methodology are presented along with significant discussion of a competitive C–S bond activation by this catalyst system.

Publisher's Statement

© ACS 2016. This is the author's version of the work. It is posted here by permission of ACM for your personal use. Not for redistribution. The final published version can be found here: http://pubs.acs.org/doi/abs/10.1021/acs.orglett.6b03249

Citation

Schmink, J.R. et al. 2016. Palladium-Catalyzed Synthesis of Aryl Vinyl Sulfides via 1,3-Oxathiolanes As Vinyl Sulfide Surrogates. Organic Letters 18.24:6360-6363.

DOI

http://www.doi.org/10.1021/acs.orglett.6b03249