Copper-catalyzed extended Pummerer reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides with an accompanying oxygen rearrangement

Kei Murakami; Junichi Imoto; Hiroshi Matsubara; Suguru Yoshida; Hideki Yorimitsu; Koichiro Oshima

doi:10.1002/chem.201204072

Copper-catalyzed extended Pummerer reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides with an accompanying oxygen rearrangement

Chemistry. 2013 Apr 26;19(18):5625-30. doi: 10.1002/chem.201204072. Epub 2013 Mar 5.

Authors

Kei Murakami¹, Junichi Imoto, Hiroshi Matsubara, Suguru Yoshida, Hideki Yorimitsu, Koichiro Oshima

Affiliation

¹ Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, Japan.

PMID: 23463458
DOI: 10.1002/chem.201204072

Abstract

The first examples of metal-catalyzed extended Pummerer reactions through the activation of sulfoxides are described. The copper-catalyzed reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ-disulfanyl-β,γ-unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4-dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Alkynes / chemistry*
Catalysis
Copper / chemistry*
Ethylenes / chemistry*
Ketones / chemistry*
Molecular Structure
Oxygen / chemistry*
Sulfides / chemistry*
Sulfoxides / chemistry*

Substances

Alkynes
Ethylenes
Ketones
Sulfides
Sulfoxides
Copper
ketene
Oxygen