School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan.
J Org Chem. 2010 Feb 19;75(4):1259-65. doi: 10.1021/jo902641g.
Silyl methide species in situ generated from 1,1,3,3-tetrakis(trifluoromethanesulfonyl)propane (Tf(2)CHCH(2)CHTf(2)) performed as an excellent acid catalyst for the vinylogous Mukaiyama-Michael reaction of alpha,beta-unsaturated ketones with 2-silyloxyfurans. Notably, the required loading of Tf(2)CHCH(2)CHTf(2) to obtain the 1,4-adducts in reasonable yield was significantly low (from 0.05 to 1.0 mol %). This carbon acid-mediated VMM reaction provides a powerful synthetic methodology to construct highly substituted gamma-butenolide structure.
原位生成的甲硅烷基甲烷物种，由 1,1,3,3-四(三氟甲磺酰基)丙烷（Tf(2)CHCH(2)CHTf(2)）作为一种出色的酸催化剂，用于α,β-不饱和酮与 2-硅氧基呋喃的烯醇式 Mukaiyama-Michael 反应。值得注意的是，获得合理产率的 1,4-加成产物所需的 Tf(2)CHCH(2)CHTf(2)用量非常低（从 0.05 到 1.0 摩尔%）。这种碳酸介导的 VMM 反应为构建高度取代的γ-丁烯内酯结构提供了一种强大的合成方法。
