Gold-Catalyzed Intermolecular Reactions of Propiolic Acids with Alkenes: [4 + 2] Annulation and Enyne Cross Metathesis

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• 作者：Hyun-Suk Yeom ; Jaeyoung Koo ; Hyun-Sub Park ; Yi Wang ; Yong Liang ; Zhi-Xiang Yu ; Seunghoon Shin
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：January 11, 2012
• 年：2012
• 卷：134
• 期：1
• 页码：208-211
• 全文大小：365K
• 年卷期：v.134,no.1(January 11, 2012)
• ISSN：1520-5126

文摘

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 伪,尾-unsaturated 未-lactones, for which preliminary asymmetric reactions were also demonstrated. For 1,2-disubstituted alkenes, unprecedented enyne cross metathesis occurred to give 1,3-dienes in a completely stereospecific fashion. DFT calculations and experiments indicated that the cyclobutene derivatives are not viable intermediates and that the steric interactions during concerted 蟽-bond rearrangements are responsible for the observed unique stereospecificity.