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Solvent-Controlled Diastereoselective Synthesis of Cyclopentane Derivatives by a [3 + 2] Cyclization Reaction of α,β-Disubstituted (Alkenyl)(methoxy)carbene Complexes with Methyl Ketone Lithium Enolates

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journal contribution
posted on 2003-02-04, 00:00 authored by José Barluenga, Jorge Alonso, Francisco J. Fañanás
Reaction of α,β-unsaturated methoxycarbene complexes 1 and 11 with methyl ketone lithium enolates 2 leads to the corresponding five-membered carbocyclic compounds 4 or diast-4 and 12. The influence of the solvent and/or cosolvent (PMDTA), which turned out to be crucial to direct the reaction to 4 or diast-4, is studied, and a tentative mechanism according to these facts is proposed. In addition, the reaction of carbene complex 1a with alkynyl methyl ketone lithium enolates can be directed to the formal [3 + 2] or [4 + 1] cyclization products by a slight variation of the reaction conditions. Finally, consecutive three-component coupling reactions with carbene complex 1a, lithium enolates 2, and aldehydes 18 to give, in a diastereoselective way, hydroxy carbonyl compounds 19 and tricyclic polyethers 20 are presented.