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The first enantioselective Nazarov cyclization of substrates with only one coordinating site and with proton-transfer as an enantioselective-determining step was realized by means of cooperative catalysis with a Lewis acid and a chiral Brønsted acid., Enantioselective control of the chirality of a tertiary α-carbon in the products of a Nazarov cyclization of enones is challenging because the reaction involves an enantioselective proton transfer process. We herein report the use of cooperative catalysis using Lewis acids and chiral Brønsted acids to control the stereochemistry of the tertiary α-carbon in the products of this reaction. Specifically, with ZnCl2 and a chiral spiro phosphoric acid as catalysts, we realized the first enantioselective construction of cyclopenta[b]indoles with chiral tertiary α-carbons via Nazarov cyclization of indole enone substrates with only one coordinating site. Mechanistic studies revealed that the chiral spiro phosphoric acid acts as a multifunctional catalyst: it co-catalyzes the cyclization of the dienone and enantioselectively catalyzes a proton transfer reaction of the enol intermediate. This new strategy of enantioselective control by means of cooperative catalysis may show utility for other challenging asymmetric cyclization reactions.

The first regioselective catalytic asymmetric [3 + 2] cycloaddition of benzofuranone-derived olefins with allenoates and substituted allenoates has been developed in the presence of (R)-SITCP., The first regioselective catalytic asymmetric [3 + 2] cycloaddition of benzofuranone-derived olefins with allenoates and substituted allenoates has been developed in the presence of (R)-SITCP, affording different functionalized 3-spirocyclopentene benzofuran-2-ones in good yields with high enantioselectivities under mild conditions. The substrate scope has also been examined. The regioselective outcomes for this phosphine-catalyzed [3 + 2] cycloaddition reaction can be rationalized using DFT calculations.

An asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed. A series homoallylic alchols with a chiral quaternary center were produced in high yields (up to 97%) and high enantioselectivities (up to 95% ee). The reaction provided an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.