Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion

Atanu Modak, Juan V. Alegre-Requena, Louis De Lescure, Kathryn J. Rynders, Robert S. Paton, Nicholas J. Race

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated"C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.

Original languageEnglish (US)
Pages (from-to)86-92
Number of pages7
JournalJournal of the American Chemical Society
Issue number1
StatePublished - Jan 12 2022

Bibliographical note

Funding Information:
N.J.R. acknowledges financial support from the University of Minnesota, the American Chemical Society Petroleum Research Fund (PRF 60782-DNI1), and the National Institute of General Medical Sciences of the National Institutes of Health under Award R35GM137920. N.J.R. also acknowledges the NIH Shared Instrumentation Grant S10OD011952. R.S.P. acknowledges financial support from the National Science Foundation under Grant 1955876 and the RMACC Summit supercomputer, supported by the National Science Foundation (ACI-1532235 and ACI-1532236), the University of Colorado Boulder and Colorado State University, and the Extreme Science and Engineering Discovery Environment (XSEDE) through allocation TG-CHE180056.

Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.


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