Cyclization-oxidation of 1,6-enyne derivatived from Baylis-Hillman adducts via Pd(II)/Pd(IV)-catalyzed reactions: stereoselective synthesis of multi-substituted bicyclo[3.1.0] hexanes and insight into reaction pathways

Cyclization-oxidation of Baylis-Hillman adducts provides a convenient method to stereoselectively synthesize variety of multi-substituted bicyclo[3.1.0] ring systems via Pd(II)/Pd(IV)-catalyzed reactions. We also disclose that C-Pd(IV) intermediate can undergo reductive elimination through S(N)2-type attack by the latent nucleophile of vinyl acetate to afford C-sp3-C-sp3 bond formation with inversion of configuration at the Pd(IV)-bounded carbon. (C) 2008 Elsevier Ltd. All rights reserved.