Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes

  1. Barluenga, J. 1
  2. Rodríguez, F. 1
  3. Vadecard, J. 1
  4. Bendix, M. 1
  5. Fañanas, F.J. 1
  6. López-Ortiz, F. 2
  7. Rodríguez, M.A. 3
  1. 1 Universidad de Oviedo
    info

    Universidad de Oviedo

    Oviedo, España

    ROR https://ror.org/006gksa02

  2. 2 Universidad de Almería
    info

    Universidad de Almería

    Almería, España

    ROR https://ror.org/003d3xx08

  3. 3 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

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Journal:
Journal of the American Chemical Society

ISSN: 0002-7863

Year of publication: 1999

Volume: 121

Issue: 38

Pages: 8776-8782

Type: Article

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DOI: 10.1021/JA991161+ SCOPUS: 2-s2.0-0043029026 WoS: WOS:000083032500013 GOOGLE SCHOLAR

More publications in: Journal of the American Chemical Society

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Abstract

In-situ-generated dialkylboroxy and diaminoboroxy Fischer carbene complexes lead to oxaborolane or oxazaborolidine derivatives via an intramolecular C-H insertion reaction. Further oxidation of these intermediates yields 1,3-diol or 1,2-amino alcohol derivatives. Diastereoselectivities as high as 99% are reached when starting from boroxy Fischer carbene complexes derived from terpenes, which represents a regio- and diastereoselective modification of this type of natural product. The influence of the C(β) substituents relative to the boron atom on the reaction path is studied, and a mechanism is proposed after identification of an intermediate by NMR. In addition, theoretical calculations show the presence of a boron-metal interaction, which could result as key step to the C-H insertion reaction.