α-NITRO SULFONES. 2. CONVENIENT NEW SYNTHESIS AND SELECTED FUNCTIONAL GROUP TRANSFORMATIONS

Article abstract of DOI:10.1021/jo00317a023

(Phenylsulfonyl)nitromethane (1) is preferentially C-alkylated by benzylic halides and primary alkyl iodides, affording secondary α-nitro sulfone products. α-Nitro sulfones are also obtained from the corresponding C-alkylation of allylic acetates in the presence of catalytic tetrakis(triphenylphosphine)palladium.The palladium(0)-catalyzed reaction is stereospecific for geranyl and neryl acetates and is also regioselective.Desulfonation of α-nitro sulfones is readily accomplished by light-induced reduction with 1-benzyl-1,4-dihydronicotinamide (BNAH).Reduction of secondary α-nitro sulfones with 20percent aqueous titanium(III) chloride affords nitriles.Oxidation with alkaline permanganate affords carboxylic acids.