Discoveries in Sulfenic Acid Anion Chemistry

Abstract

Sulfenates, the conjugate bases of sulfenic acids are nucleophilic species that can be alkylated at sulfur to create sulfoxides. Sulfenates are generally not isolable, but must be generated and functionalized in solution. In this report, we summarize accomplishments toward the liberation of 1-alkenesulfenate anions and also the first general method for the release of alkane- and arenesulfenates. As prochiral entities, there is also potential for their stereoselective alkylation. As such, a protected cysteinesulfenate has been generated and alkylated at sulfur with dr's as high as 95:5. Also, when there is stereogenicity in the electrophile, diastereoselective alkylation of simple arenesulfenates occurs with dr's approaching and exceeding 9:1.

GRAPHICAL ABSTRACT

Keywords:

• Sulfenates
• alkylation
• diastereoselection
• sulfur nucleophile

Notes

n-BuLi is added as a solution in hexanes whereas lithium methoxide is administered as a solution in methanol.