Behaviors of α-Fluorocarbenoids Derived from the Nucleophilic Desulfinylation of α-Chloro-α-fluoroalkyl Sulfoxides

Article abstract of DOI:10.1246/bcsj.65.210

2-Aryl-1-chloro-1-fluoroethyl sulfoxides underwent nucleophilic desulfinylation with PhMgBr to give (Z)-fluorostyrene derivatives in a very stereoselective manner (>33:1) via an α-fluorocarbene species.When treated with 3 equiv of PhLi in the presence of N,N,N',N'-tetramethylethylenediamine, they similarly formed fluorostyrenes as a stereoisomeric mixture (E:Z = 2:1), but with 1 equiv of PhLi 1-aryl-1-chloro-1-fluoroethanes were the major product.On the other hand, no formation of a fluoroalkene was observed in the desulfinylation of 1-chloro-1-fluoro-4-phenylbutyl sul foxide with the nucleophiles.In the latter reaction, oxidation and/or phenylation of the intermediate carbene were the main pathways.