Insertion of Diazo Esters into C-F Bonds toward Diastereoselective One-Carbon Elongation of Benzylic Fluorides: Unprecedented BF3 Catalysis with C-F Bond Cleavage and Re-formation

Fei Wang; Yoshihiro Nishimoto; Makoto Yasuda

doi:10.1021/jacs.1c10517

Insertion of Diazo Esters into C-F Bonds toward Diastereoselective One-Carbon Elongation of Benzylic Fluorides: Unprecedented BF₃ Catalysis with C-F Bond Cleavage and Re-formation

J Am Chem Soc. 2021 Dec 15;143(49):20616-20621. doi: 10.1021/jacs.1c10517. Epub 2021 Nov 12.

Authors

Fei Wang¹, Yoshihiro Nishimoto^{1

2}, Makoto Yasuda^{1

2}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.

PMID: 34766748
DOI: 10.1021/jacs.1c10517

Abstract

Selective transformation of C-F bonds remains a significant goal in organic chemistry, but C-F insertion of a one-carbon-atom unit has never been established. Herein we report the BF₃-catalyzed formal insertion of diazo esters as one-carbon-atom sources into C-F bonds to accomplish one-carbon elongation of benzylic fluorides. A DFT calculation study revealed that the BF₃ catalyst could contribute to both C-F bond cleavage and re-formation. This elongation provided α-fluoro-α,β-diaryl esters with a high level of diastereoselectivity. Various benzylic fluorides and diazo esters were applicable. The synthetic utility of this method was demonstrated by the synthesis of a fluoro analogue of a compound that is used as a transient receptor and potential canonical channel inhibitor.

Publication types

Research Support, Non-U.S. Gov't