Gold-Catalyzed Intermolecular Reactions of Propiolic Acids with Alkenes: [4 + 2] Annulation and Enyne Cross Metathesis
作者:Hyun-Suk Yeom、Jaeyoung Koo、Hyun-Sub Park、Yi Wang、Yong Liang、Zhi-Xiang Yu、Seunghoon Shin
DOI:10.1021/ja210792e
日期:2012.1.11
A gold-catalyzed intermolecular reaction of propiolic acids with alkenes led to a [4 + 2] annulation or enyne cross metathesis. The [4 + 2] annulation proceeds with net cis-addition with respect to alkenes and provides an expedient route to α,β-unsaturated δ-lactones, for which preliminary asymmetric reactions were also demonstrated. For 1,2-disubstituted alkenes, unprecedented enyne cross metathesis
丙炔酸与烯烃的金催化分子间反应导致 [4 + 2] 环化或烯炔交叉复分解。[4 + 2] 环化与烯烃的净顺式加成一起进行,并为 α,β-不饱和 δ-内酯提供了便利的途径,也证明了初步的不对称反应。对于 1,2-二取代烯烃,前所未有的烯炔交叉复分解反应以完全立体定向的方式得到 1,3-二烯。DFT 计算和实验表明,环丁烯衍生物不是可行的中间体,协同 σ 键重排期间的空间相互作用是观察到的独特立体特异性的原因。