DOI: 10.1055/a-2136-3609 ISSN: 0936-5214

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

Yoshihiro Nishimoto, Makoto Yasuda
  • Organic Chemistry

Abstract

In 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 Introduction

2 Acetate/Alkoxide Shuttle: Insertion Reaction of α-Diazo Esters into a Carbon–Carbon Bond of Alkyl Acetates, Alkyl Ethers, and Acetals

3 Halide Shuttle: Insertion Reaction of α-Diazo Esters into a Carbon–Carbon Bond of Alkyl Halides

4 Halide Shuttle: Insertion of α-Diazo Esters into a Carbon–Halogen Bond of Alkyl Halides

5 Conclusion

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