Mechanistic Insight into Additions of Allylic Grignard Reagents to Carbonyl Compounds

Nicole D. Bartolo, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

Allylic Grignard reagents exhibit high reactivity and low selectivity in additions to carbonyl compounds. Additions of allylic Grignard reagents to carbonyl compounds were investigated using prenylmagnesium chloride as a mechanistic probe. When the carbonyl group is relatively unhindered, the addition proceeds through a six-membered transition state with allylic transposition. This process generally occurs with no diastereoselectivity because the reaction rates approach the diffusion limit. With hindered ketones, however, this pathway is disfavored, and the addition proceeds through a transition state resembling that of other Grignard reagents.

Original languageEnglish (US)
Pages (from-to)10197-10206
Number of pages10
JournalJournal of Organic Chemistry
Volume83
Issue number17
DOIs
StatePublished - Sep 7 2018

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Carbonyl compounds
Ketones
Reaction rates
Chlorides

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Mechanistic Insight into Additions of Allylic Grignard Reagents to Carbonyl Compounds. / Bartolo, Nicole D.; Woerpel, Keith.

In: Journal of Organic Chemistry, Vol. 83, No. 17, 07.09.2018, p. 10197-10206.

Research output: Contribution to journalArticle

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