Chemistry of Sulfines, Part V: Chemo- and Stereoselective Synthesis and Hetero-Diels–Alder Reactions of Stable Sulfines

Abstract

The stereoselective synthesis of a variety of Z-sulfines by the oxidation of organic trithiocarbonates with m-chloroperbenzoic acid (m-CPBA) is described. Transient E-sulfines that are formed upon heating of Z-sulfines during cycloaddition reactions were trapped with 2,3-dimethyl-1,3-butadiene to yield only one of the possible diastereomers of the functionalized cyclic allylic sulfoxides. An X-ray analysis and ab initio calculations were performed to provide insight into the steric course of the oxidation and cycloaddition reactions.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional tables and figures.]

GRAPHICAL ABSTRACT

Keywords:

• Chlorodithioformates
• trithiocarbonates
• oxidation
• sulfines
• Diels–Alder
• 1,3-dienes
• thiopyran S-oxides
• X-ray
• Ab initio calculations

Acknowledgments

Partial financial support from Danish International Development Agency (DANIDA) is highly appreciated.