Ye Longwu, Zhang Liming
Department of Chemistry, University of Nevada, Reno, Nevada 89557, USA.
Org Lett. 2009 Aug 20;11(16):3646-9. doi: 10.1021/ol901346k.
An efficient synthesis of alpha-iodo/bromo-alpha,beta-unsaturated aldehydes/ketones directly from propargylic alcohols is described. This reaction is catalyzed collaboratively by two metal complexes, Ph(3)PAuNTf(2) and MoO(2)(acac)(2), and Ph(3)PO as an additive helps suppress undesired enone/enal formation. Notable features of this method include low catalyst loadings, mild reaction conditions, and mostly good to excellent diastereoselectivity. In comparison with our previously developed method based on propargylic acetate substrates, this chemistry omits the need to prepare acetate derivatives and, moreover, has a much broader substrate scope.
本文描述了一种直接从炔丙醇高效合成α-碘代/溴代-α,β-不饱和醛/酮的方法。该反应由两种金属配合物Ph(3)PAuNTf(2)和MoO(2)(acac)(2)协同催化，Ph(3)PO作为添加剂有助于抑制不需要的烯酮/烯醛的形成。该方法的显著特点包括催化剂负载量低、反应条件温和，并且大多数情况下具有良好到优异的非对映选择性。与我们之前基于炔丙基乙酸酯底物开发的方法相比，这种方法无需制备乙酸酯衍生物，而且底物范围更广。
