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Conjugate addition of organocuprates on γ-methyl-δ-oxy-α,β-enones. Influence of the alkoxy substituent on the diastereoselection

Publié dansJournal of organometallic chemistry, vol. 423, no. 2, p. 281-305
Date de publication1992
Résumé

The stereochemistry of the conjugate addition of cuprates to the title compounds is mainly governed by the ?-methyl group, but the alkoxy substituent also plays a role. A ?-methyl group exerts the dominant effect in the conjugate addition of a cuprate on a ?-methyl-d-oxy-a,ß-enone, leading to pure anti-addition to the syn substrate, whereas for the anti substrate, a chelating group on oxygen (MEM) definitely assists anti addition. The syn enone reacts exclusively according to the Morokuma model, whereas the anti enone exhibits a chelate effect and fits better with the Isobe model. In both cases, capture of the enolate by iodomethane is stereoselective, so that four contiguous substituted carbons can be created from the initial two, with good stereoselectivity.

Structure d'affiliation Pas une publication de l'UNIGE
Citation (format ISO)
COURTEMANCHE, Gilles et al. Conjugate addition of organocuprates on γ-methyl-δ-oxy-α,β-enones. Influence of the alkoxy substituent on the diastereoselection. In: Journal of organometallic chemistry, 1992, vol. 423, n° 2, p. 281–305. doi: 10.1016/0022-328X(92)83121-W
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ISSN du journal0022-328X
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Création21.06.2010 14:44:12
Première validation21.06.2010 14:44:12
Heure de mise à jour14.03.2023 15:48:15
Changement de statut14.03.2023 15:48:15
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