Etude de l'action d'organometalliques sur la cetone CH3COCHCHCHCHCH3. Application a la preparation de cetones β-ethyleniques a partir d'organocuprates lithiens

Barbot, F.; Kadib-Elban, A.; Miginiac, Ph.

doi:10.1016/0022-328x(83)80167-3

Cited by 31 publications

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“…Syntheses and characterization data are available for compounds 1 or 9a , , 9b , , 9c , ,− 10a , ,− 10b , ,, 10c , ,, 11cA , , 11cB , 21b , 22 , and 28 , from the corresponding references.…”

Section: Methodsmentioning

confidence: 99%

Regioselective 1,4-Conjugate Addition of Grignard Reagents to α,β–γ,δ-Dienones and α,β–γ,δ-Dienyl Thiol Esters

Amoah

Dieter

2017

J. Org. Chem.

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Alkyl Grignard reagents (Et, Bu,Pr, cyclohexyl), with the exception of BuMgCl, undergo exclusive or exceptionally highly regioselective 1,4-addition reactions to α,β-γ,δ-unsaturated ketones, while aryl and heteroaryl Grignard reagents give mixed results ranging from exclusive 1,4-addition (1-naphthyl, 2-N-methylpyrrolyl) to regioselective 1,2-addition (2-furyl, 2:1). All alkyl, aryl, and heteroaryl Grignard reagents examined gave exclusive 1,4-addition reactions with α,β-γ,δ-unsaturated thiol esters, with the exception ofBuMgCl, which gave an 80:20 mixture of 1,4:1,6-addition products. The high chemo- and regioselectivity observed for these reactions is attributed to a radical or radical-like pathway for the alkyl Grignard reagents and possibly a carbanion pathway for aryl Grignard reagents. The α,γ-dienyl thiol esters provide for a one-pot tandem 1,4-addition-nucleophilic acyl substitution reaction sequence to afford 3-substituted 4-enone moieties.

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