alpha,beta-Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5-Alkoxy Migration of 1,6-Enynes: Mechanisms and Applications

作者:Calleja Pilar; Pablo Oscar; Ranieri Beatrice; Gaydou Morgane; Pitaval Anthony; Moreno Maria; Raducan Mihai; Echavarren Antonio M*
来源:Chemistry - A European Journal, 2016, 22(38): 13613-13618.
DOI:10.1002/chem.201602347

摘要

1,6-Enynes bearing OR groups at the propargyl position generate alpha,beta-unsaturated gold(I)-carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3-diketones to give products of alpha-alkylation. The best migrating group is p-nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)-schisanwilsonene A has been accomplished. The different competitive reaction pathways have been delineated computationally.

  • 出版日期2016-9