Iron-catalyzed carbometalation of propargylic and homopropargylic alcohols

Donghui Zhang, Joseph M. Ready

Research output: Contribution to journalArticle

91 Citations (Scopus)

Abstract

Nucleophilic addition to alkynes represents an attractive approach to the synthesis of olefins. Obstacles to this strategy include the low reactivity of alkynes toward many organometallic reagents and difficulties associated with controlling the regioselectivity of addition. Here we demonstrate that Fe(III) salts are effective precatalysts for the carbometalation of alkynes. Primary and secondary propargylic and homopropargylic alcohols react with alkyl and aryl Grignard reagents to provide Z-allylic and -homoallylic alcohols as single stereo and regioisomers. Alkylation and arylation occur distal to the alcohol. Common oxygen protecting groups and tertiary nitrogens are tolerated. The intermediate vinyl magnesium or iron species can be trapped with a variety of electrophiles including aldehydes, allyl bromide, and N-bromosuccinimide. Diyne substrates undergo an unusual addition/cyclization reaction to generate cyclic dienes. A brief discussion of mechanism is included.

Original languageEnglish (US)
Pages (from-to)15050-15051
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number47
DOIs
StatePublished - Nov 29 2006

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Alkynes
Alcohols
Iron
Bromosuccinimide
Regioselectivity
Cyclization
Alkylation
Alkenes
Organometallics
Aldehydes
Magnesium
Olefins
Nitrogen
Salts
Oxygen
Substrates

ASJC Scopus subject areas

  • Chemistry(all)

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Iron-catalyzed carbometalation of propargylic and homopropargylic alcohols. / Zhang, Donghui; Ready, Joseph M.

In: Journal of the American Chemical Society, Vol. 128, No. 47, 29.11.2006, p. 15050-15051.

Research output: Contribution to journalArticle

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