Catalaytic Isomerization of 1,5Enynes to （Catalaytic异构化的5Enynes）.pdf

Published on Web 08/13/2004 Catalaytic Isomerization of 1,5-Enynes to Bicyclo[3.1.0]hexenes Michael R. Luzung, Jordan P. Markham, and F. Dean Toste* Center for New Directions in Organic Synthesis, Department of Chemistry, Uniersity of CaliforniaBerkeley, Berkeley, California 94720 Received June 24, 2004; E-mail: fdtoste@ Transition metal-catalyzed isomerization and rearrangement Table 1. Au(I)-Catalyzed Synthesis of Bicyclo[3.1.0]hexenesa reactions of unsaturated systems provide access to structural motifs not accessible through their thermal counterparts. This is exempli- fied by the numerous applications of transition metal-catalyzed Alder-ene reactions of 1,6- and 1,7-enynes for the synthesis of cyclopentyl and cyclohexyl ring systems.1 The corresponding skeletal rearrangements of simple 1,5-enynes are much less studied. Berson and co-workers conjectured that the thermal rearrangement of 1,5-enyne 1 proceeds via bicyclo[3.1.0]hexene 2 to afford toluene and triene 3 as the major constituents of a complex mixture.2 Scat- tered reports of transition metal-catalyzed isomerizations of 1,5-en- 3 ynes exist; however, these generally employ enol ethers as the ene component.4,5 While enols are expected to be excellent nucleo- philes,6 we were intrigued by the possibility that metal alkyne complexes could be electrophilic enough to react even with simple olefins and catalyze processes related to the thermal rearrangement. To this end, treatment of 1,5-enyne 4 with 1 mol % palladium- (II) or platinum(II) complexes returned mainly starting material (eq 2). Both silver(I) tetrafluorobor