Sulfene

It is the simplest member of the sulfenes, the group of compounds which are S,S-dioxides of thioaldehydes and thioketones, and have the general formula R2C=SO2.

[1][2][3] The first general method for preparation of sulfene as an intermediate, reported simultaneously in 1962 by Gilbert Stork[4] and by Günther Optiz,[5] involved the removal of hydrogen chloride from methanesulfonyl chloride using triethylamine in the presence of an enamine as trapping agent.

A simple alternative which avoids the use of amines involves desilylation of trimethylsilylmethanesulfonyl chloride with cesium fluoride in the presence of trapping agents.

Sulfenes react with enamines, ynamines, and 1,3-cyclopentadienes to give thietanes, thietes and Diels-Alder adducts, respectively.

In the presence of a chiral tertiary amine complex, several sulfenes could be trapped with trichloroacetaldehyde (chloral) in a catalytic asymmetric synthesis of β-sulfones (four-membered ring sulfonate esters).

Skeletal formula of sulfene with both explicit hydrogens added
Skeletal formula of sulfene with both explicit hydrogens added
Spacefill model of sulfene
Spacefill model of sulfene
Structure of thioureadioxide ((H 2 N) 2 CSO 2 ). Selected distances and angles: r S=O = 1.49, r S=C = 1.85.1, r C-N = 1.31 Å, sum of angles around S = 312.4°. [ 7 ]