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The catalytic asymmetric ene reaction with difluoropyruvate as an electrophile in the presence of a dicationic palladium complex is shown. This is the reliable and practical catalytic asymmetric synthesis for various α-CF2H tertiary alcohols in high yields and enantioselectivities. The reaction with isobutene can be catalyzed efficiently under solvent-free conditions with low catalyst loading (up to S/C 2000). Furthermore, difluoropyruvate is applicable to the [2 + 2] cycloaddition reaction in high yields and enantioselectivities.

Scheme 1. Regio-and enantioselective Friedel-Crafts type reactions with dicationic palladium catalyst 2. Results and discussion Initially, the Friedel-Crafts type reaction of 2-trimethylsilyl furan 4a as a nucleophile was examined in the presence of

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