Acetate/Alkoxide/Halide Shuttle Systems Mediated by Lewis Acid Catalysts for Insertion Reaction of a One-Carbon Unit into Carbon–Carbon or Carbon–Halogen Bonds

Abstract

AbstractIn this account, we describe our research on a Lewis acid-catalyzed insertion reaction of α-diazo esters into a carbon–carbon or carbon–halogen bond. Indium catalysts mediated not only the insertion of α-diazo esters into a carbon–carbon bond of alkyl acetates, alkyl ethers, acetals, and alkyl halides, but also a carbon–halogen bond of alkyl chlorides, bromides, and iodides. BF3 specifically accelerated the insertion of α-diazo esters into a carbon–fluorine bond. The key to this catalysis is acetate, alkoxide, and halide shuttle systems mediated by a Lewis acid, in which the Lewis acid abstracts a leaving group from a starting substrate and releases the leaving group to the appropriate carbocation intermediate in the catalytic cycle.1 Introduction2 Acetate/Alkoxide Shuttle: Insertion Reaction of α-Diazo Esters into a Carbon–Carbon Bond of Alkyl Acetates, Alkyl Ethers, and Acetals3 Halide Shuttle: Insertion Reaction of α-Diazo Esters into a Carbon–Carbon Bond of Alkyl Halides4 Halide Shuttle: Insertion of α-Diazo Esters into a Carbon–Halogen Bond of Alkyl Halides5 Conclusion