Catalytic Asymmetric Arylation of 伪-Aryl-伪-diazoacetates with Aniline Derivatives

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• 作者：Bin Xu ; Mao-Lin Li ; Xiao-Dong Zuo ; Shou-Fei Zhu ; Qi-Lin Zhou
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：July 15, 2015
• 年：2015
• 卷：137
• 期：27
• 页码：8700-8703
• 全文大小：424K
• ISSN：1520-5126

文摘

The asymmetric arylation of diazo compounds with aniline derivatives cooperatively catalyzed by an achiral dirhodium complex and a chiral spiro phosphoric acid is reported. The reaction provides a new method for the facile synthesis of 伪-diarylacetates, versatile building blocks with a diaryl tertiary chiral center, in good yields (up to 95%) with high enantioselectivities (up to 97% ee). Preliminary mechanistic studies suggest that the arylation reaction proceeds via a stepwise process, in which the enantioselectivity is controlled by a chiral spiro phosphoric acid-promoted proton shift in a zwitterionic intermediate. This work represents the first asymmetric intermolecular C(sp²)鈥揌 bond insertion reaction with arenes.