Influence of steric hindrance on the 1,4- versus 1,6-Michael addition: synthesis of furans and pentasubstituted benzenes.

Abstract

We described the influence of steric hindrance on the 1,4- versus 1,6-Michael addition reaction on 2-(3,3-bis(methylthio)-1-arylallylidene)malononitriles. An efficient and direct synthesis of trisubstituted furans was achieved through the reaction of 2-(3,3-bis(methylthio)-1-arylallylidene)malononitriles and acetone under mild conditions in good to moderate yield by the 1,4-Michael addition. Further exploration of the reaction with a sterically hindered aryl group containing 2-(3,3-bis(methylthio)-1-arylallylidene)malononitriles afforded biaryls by an in situ generated nucleophile through the 1,6-Michael addition. The synthetic utility of furan is further explored. These precursors are easily accessible from aryl methyl ketones. Various functional groups like alkyl, aryl, nitrile, amine, aroyl, and thiomethyl can be directly installed in the benzene and furan rings. A one-pot approach for the construction of a benzene nucleus was also developed. The structure of two compounds was confirmed by X-ray crystallography.