Chemistry: A European Journal 2006-09-18

Diastereoselective multicomponent cyclizations of Fischer carbene complexes, lithium enolates, and allylmagnesium bromide leading to highly substituted five- and six-membered carbocycles.

José Barluenga, Iván Pérez-Sánchez, Marcos G Suero, Eduardo Rubio, Josefa Flórez

Index: Chemistry 12(27) , 7225-35, (2006)

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Abstract

The one-pot sequential reaction of a chromium alkoxycarbene complex, a ketone or ester lithium enolate, and allylmagnesium bromide enabled the selective synthesis of novel diastereomerically pure pentasubstituted cyclopentanols or tetrasubstituted 1,4-cyclohexanediols, depending on the degree of substitution at the Cbeta position of the enolate anion. A few exceptions have been encountered in which tetrasubstituted cyclopentanols or pentasubstituted 1,4-cyclohexanediols were selectively formed. The use of 2-iodoethoxycarbene complexes gave access to 1,2,4-cyclohexanetriols. These multicomponent-coupling reactions involved the formation of lithium alkylpentacarbonylchromates as key intermediates, which further evolved through intramolecular processes, such as insertion of an alkene, CO insertion or addition to a carbonyl group, and, moreover, could be trapped in intermolecular reactions with different electrophiles and styrene. The substitution pattern of the alkylchromate carbon chain has been proposed to control the nature of the annulation process.