The vinylogous intramolecular Morita-Baylis-Hillman reaction: Synthesis of functionalized cyclopentenes and cyclohexenes with trialkylphosphines as nucleophilic catalysts

The development of the vinylogous intramolecular Morita-Baylis-Hillman reaction for the synthesis of functionalized cyclopentenes and cyclohexenes is described. The reaction involves the trialkyphosphine-catalyzed cyclization of 1,6- or 1,7-diactivated 1,5-hexadienes or 1,6-heptadienes, containing carboxyaldehyde, methyl ketone, or methoxycarbonyl as the olefin activating groups. A representative example of this reaction is the Me3P-catalyzed cyclization of 1a in tert-amyl alcohol, which provides the substituted cyclopentene 2a in 95% yield and with 97:3 regioselectivity. Copyright © 2002 American Chemical Society.