Li Shou-Lei, Yang Chen, Wu Quan, Zheng Han-Liang, Li Xin, Cheng Jin-Pei
State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry , Nankai University , Tianjin 300071 , P. R. China.
J Am Chem Soc. 2018 Oct 10;140(40):12836-12843. doi: 10.1021/jacs.8b06014. Epub 2018 Sep 28.
A highly efficient method to access axially chiral anilides through asymmetric allylic alkylation reaction with achiral Morita-Baylis-Hillman carbonates by using a biscinchona alkaloid catalyst was reported. Through the atroposelective approach, a broad range of axially chiral anilide products with different acyl groups, such as substituted phenyl, naphthyl, alkyl, enyl, styryl, and benzyl, were generated with very good yields, moderate to excellent cis: trans ratios, and good to excellent enantioselectivities. The reaction can be scaled up, and the synthetic utility of axially chiral anilides was proved by transformations. Moreover, the linear free energy relationship analysis was introduced to investigate the reaction.
报道了一种高效的方法，通过使用双金鸡纳生物碱催化剂，使非手性的森田-贝利斯-希尔曼碳酸酯进行不对称烯丙基烷基化反应来制备轴手性酰胺。通过该阻转选择性方法，生成了一系列具有不同酰基的轴手性酰胺产物，如取代苯基、萘基、烷基、烯基、苯乙烯基和苄基，产率很高，顺反比适中至优异，对映选择性良好至优异。该反应可以放大规模，并且通过转化证明了轴手性酰胺的合成实用性。此外，引入了线性自由能关系分析来研究该反应。
