Palladium catalyzed decarboxylative cross-coupling reactions of less stabilized carbon nucleophiles with secondary benzyl electrophiles is presented. Specifically, a stereospecific decarboxylative benzylation reaction has been developed for the sp-sp3 coupling of in-situ generated acetylide anions with chiral benzyl palladium intermediates to generate diarylmethane containing alkynes in high enantiospecificity (Scheme 1). Furthermore, secondary benzyl isopropenyl carbonates undergo facile decarboxylation to form arylated ketones via the likely intermediacy of Pd-π-benzyl complexes. In addition, appropriate modification of the palladium catalyst allows the isolation of the dearomatized keones in high yield (Scheme 2). In these cross-coupling reactions, CO2 is eliminated as the sole byproduct and avoid the use of strongly basic reagents or toxic benzyl halides.

Palladium-catalyzed decarboxylative C–C bond formation of secondary benzyl electrophiles

249th National Meeting (2015)

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