Tomofumi Takuwa

Indium-Mediated Reaction of 3-Bromo-3,3-difluoropropene and Bromodifluoromethylacetylene Derivatives with Aldehydes

Abstract Aldehydes reacted with 3-bromo-3,3-difluoropropene at the α-position in the presence of indium to afford 1-substituted-2,2-difluorobut-3-en-1-ols. Ketones and other electrophiles are inert under the examined conditions. The reaction of bromodifluoromethylacetylene derivatives with an aldehyde in the presence of indium provided difluorohomopropargylic alcohols. These reactions efficiently proceeded in polar solvents (water, DMF) under mild conditions.

Efficient synthesis of (R)- and (S)-1-amino-2,2-difluorocyclopropanecarboxylic acid via lipase-catalyzed desymmetrization of prochiral precursors

The asymmetric syntheses of (+)-(R)-1-amino-2,2-difluorocyclopropane-1-carboxylic acid and its enantiomer have been accomplished. Key reactions in the synthetic design are lipase-catalyzed desymmetrization of a prochiral diol and a prochiral diacetate.

α,α-difluoroallyl carbanion: Indium-mediation in its facile coupling with aldehydes

Indium-mediated coupling of aldehydes with 3-bromo-3,3-difluoropropene gives 1-substituted-2,2-difluorobut-3-en-1-ols in high yields at room temperature. The coupling takes place at the gem-difluorocarbon selectively. Ketones are inert under the conditions examined.

Novel Fluorination of Small-ring Tertiary Cycloalkanols: Reaction of Diethylaminosulfur Trifluoride with Tertiary Cyclobutanols

The reaction of diethylaminosulfur trifluoride with a tertiary cyclobutanol afforded a fluorocyclobutane, a (fluoromethyl)cyclopropane or a homoallylic fluoride.