Allylic functionalization of unactivated olefins with grignard reagents

Hongli Bao, Liela Bayeh, Uttam K. Tambar

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods. It all begins with olefins: Allylic functionalization with carbon nucleophiles is a powerful strategy for converting unactivated olefins into complex products. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents.

Original languageEnglish (US)
Pages (from-to)1664-1668
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number6
DOIs
StatePublished - Feb 3 2014

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Alkenes
Olefins
Nucleophiles
Alkylation
Carbon
Copper
Regioselectivity
Biological Products

Keywords

  • alkenes
  • allylic compounds
  • copper
  • Grignard reaction
  • homogeneous catalysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Allylic functionalization of unactivated olefins with grignard reagents. / Bao, Hongli; Bayeh, Liela; Tambar, Uttam K.

In: Angewandte Chemie - International Edition, Vol. 53, No. 6, 03.02.2014, p. 1664-1668.

Research output: Contribution to journalArticle

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