Unprecedented Noncatalyzed anti-Carbozincation of Diethyl Acetylenedicarboxylate through Alkylzinc Group Radical Transfer

Julien Maury, Laurence Feray* and Michele P. Bertrand*

*Laboratoire Chimie Provence, UMR 6264, Equipe CMO, case 562, Universite Aix-Marseille, FST Saint-Jerome, av. Escadrille Normandie Niemen, 13397 Marseille cedex 20, France, Email: laurence.ferayuniv-cezanne.fr, michele.bertranduniv-cezanne.fr

J. Maury, L. Feray, M. P. Bertrand, Org. Lett., 2011, 13, 1884-1887.

DOI: 10.1021/ol200419x

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Abstract

A radical carbozincation of diethyl acetylenedicarboxylate in the presence of air leads to fumaric derivatives through a selective alkylzinc group radical transfer controlled by coordination. The total trans stereocontrol is unprecedented, carbocupration is well-known to give the reversal selectivity at low temperature, while classical radical addition methodologies lead to mixtures of isomers.

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Key Words

unsaturated esters, iodination

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ID: J54-Y2011-0950