Nucleophilic Desulfinylation of [alpha]-Fluoro-[beta]-(alkoxy and silyloxy) Sulfoxides.Effects of the [beta]-Oxy Substituents on Protonation, 1,2-Hydrogen Migration, and Nucleophile Addition to the Fluorocarbenoid Centers

• Published in: Bulletin of the Chemical Society of Japan Vol. 65; no. 1; p. 218
• Main Authors: Uno, Hidemitsu, Sakamoto, Katsuji, Suzuki, Hitomi
• Format: Journal Article
• Language: English
• Published: Tokyo Chemical Society of Japan 01.01.1992
• ISSN: 0009-2673

Treatment of 2-(4-biphenylyl)-2-t-butyldimethylsilyloxy-1-chloro-1-fluoroethyl phenyl sulfoxide with PhMgBr resulted in the formation of a fluorostilbene derivative, a fluoro enol silyl ether and small amounts of 4-(fluoroacetyl)biphenyl, while a similar reaction of 2-methoxymethoxy analog mainly led to the fluorostilbene derivatives and a simple desulfinylation product. In contrast, both sulfoxides reacted with PhLi to give chlorofluoro compounds and fluoro enol ethers. In these reactions, the stability of carbenoids derived from the nucleophilic removal of the sulfoxide moiety was greatly affected by the β-substituents, thus controlling the product distributions.