Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Abstract

We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides that is catalyzed by organophosphanes in the presence of base. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under mild, metal-free conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/rearrangement sequence. Mechanistic investigations revealed that C–O bond cleavage on a possible betaine intermediate is the key step for the installation of the keto-functionality at the β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by a scale-up reaction and synthetic transformations of the products.

Key words

β-acylation - functionalized 2-ylideneoxindoles - indolin-3-ones - phospha-Michael addition - phosphine catalysis

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