Synthesis of Allyl Carbamates through the Regioselective Domino Reaction of Amines, CO₂, and Unsymmetrical Allyl Chlorides under Pd Catalysis

The regioselective domino reaction of CO₂ (1 atm), amines, and unsymmetrical allyl chlorides in the presence of a palladium complex and K₃PO₄ under mild conditions to provide allyl carbamates in good yields with excellent regioselectivity (99:1) was accomplished. With the use of both CO₂ (1 atm) and unsymmetrical allyl chlorides, a highly regioselective three-component domino reaction is realized under mild conditions and is used in a Pd-catalyzed allylation process. This method affords new entry to a diverse set of allyl carbamates; dppf = 1,1′-bis(diphenylphosphanyl)ferrocene.