Highly regio- and stereoselective (3 + 2) annulation reaction of allenoates with 3-methyleneindolin-2-ones catalyzed by a planar chiral [2.2]paracyclophane-based bifunctional phosphine-phenol catalyst.

Abstract

A planar chiral [2.2]paracyclophane-based phosphine-phenol catalyst catalyzed the (3 + 2) annulation reaction of ethyl 2,3-butadienoate with 3-methyleneindolin-2-ones to produce 2,5-disubstituted cyclopentene-fused C3-spirooxindoles in high yields with high regio-, diastereo-, and enantioselectivities. This catalyst was suitable for reactions of not only benzylideneindolinones but also alkylideneindolinones, the chiral phosphine-catalyzed reactions of which have not yet been reported. Density functional theory calculations suggested that the formation of hydrogen bonds between the phenolic OH group of the catalyst and the allenoate carbonyl group, rather than between the OH group and the carbonyl group of indolinone, contributed to the formation of an efficient reaction space at the enantiodetermining step.