Arynes Double Bond Insertion/Nucleophilic Addition with Vinylogous Amides and Carbodiimides

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• 作者：Ran Li ; Huarong Tang ; Haixing Fu ; Hailong Ren ; Xuemei Wang ; Chunrui Wu ; Chao Wu ; Feng Shi
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：February 7, 2014
• 年：2014
• 卷：79
• 期：3
• 页码：1344-1355
• 全文大小：641K
• ISSN：1520-6904

文摘

Arynes are shown to insert into some C鈺怷 double bonds, leading to benzannulated four-membered rings. The strain of these rings allow for a ready, spontaneous opening to afford o-quinomethide analogues. Subsequent nucleophilic addition re-aromatizes the intermediates to achieve ortho-difunctionalization of arynes. In this report, we describe the aryne insertion into the C鈺怌 double bonds of vinylogous amides and the C鈺怤 double bonds of carbodiimides. The correlation and comparison with aryne single bond insertion chemistry will be discussed. Computational studies for the ring-opening step, as well as the nature of the o-quinomethide intermediates, will also be discussed.