Rhenium-catalyzed regio- and stereoselective synthesis of γ-thio-α,β-unsaturated ketones via insertion of terminal alkynes into the C-S bond

Mitsumi Nishi; Yoichiro Kuninobu; Kazuhiko Takai

doi:10.1021/ol302810u

Rhenium-catalyzed regio- and stereoselective synthesis of γ-thio-α,β-unsaturated ketones via insertion of terminal alkynes into the C-S bond

Org Lett. 2012 Dec 7;14(23):6116-8. doi: 10.1021/ol302810u. Epub 2012 Nov 12.

Authors

Mitsumi Nishi¹, Yoichiro Kuninobu, Kazuhiko Takai

Affiliation

¹ Division of Chemistry and Biotechnology, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.

PMID: 23145492
DOI: 10.1021/ol302810u

Abstract

The reaction of α-thioketones and alkynes in the presence of a rhenium catalyst, [HRe(CO)(4)](n), gave γ-thio-α,β-unsaturated ketones in excellent yields. The alkynes were inserted into the carbon-sulfur bond of the α-thioketones, and isomerization of a double bond provided the products with high regio- and stereoselectivities. This reaction also proceeded in an intramolecular fashion.