有机催化吲哚与环状酮亚胺膦酸酯的傅-克反应合成含手性季碳胺基膦酸衍生物

doi:10.1016/S1872-2067(17)62804-3

摘要/Abstract

摘要：

在有机合成中，季碳中心的构建始终是一项充满挑战的课题.含手性季碳中心的胺基膦酸化合物以其多样的生物活性，如酶抑制剂、抗真菌剂、抗菌剂和抗病毒剂等，受到了科研工作者的广泛关注.目前已有许多合成策略报道，其中亲核试剂与α-酮亚胺膦酸酯的不对称加成策略为含手性季碳中心胺基膦酸衍生物的合成提供了一条简洁有效的路径，但是却鲜有报道，已有的报道也仅局限于乙酰氰、丙酮、硝基甲烷和芳基硼酸作亲核试剂.为满足多样的手性胺基膦酸衍生物的合成需求，新的合成策略和亲核源仍有待进一步发展.值得一提的是，不对称傅-克反应是一种非常有效的构建碳-碳键的合成方法，并已有广泛报道.基于吲哚与亚胺底物的傅-克反应经验，我们研究组发展了一种有机催化吲哚与环状酮亚胺膦酸酯傅-克反应合成含手性季碳胺基膦酸衍生物的方法，使用的有机催化剂是手性磷酸.通过对溶剂、催化剂和温度的筛选发现，使用在3，3'-位引入吸电子的3，5-二三氟甲基苯基取代的H8-BINOL衍生的手性磷酸作催化剂，反应温度为30 ^oC，溶剂为均三甲苯时，最高能以98%对映选择性得到含手性季碳胺基膦酸酯化合物.该反应操作简单，条件温和，不仅适用于吲哚衍生物，对吡咯也能取得较好结果.总之，该方法提供了一条简洁有效的合成手性胺基膦酸衍生物的途径.

关键词: 傅-克反应, 季碳胺基膦酸酯, 吲哚, 手性磷酸

Abstract:

An efficient asymmetric Friedel–Crafts reaction has been developed for the synthesis of optically active quaternary α-aminophosphonates with up to 98% ee. The synthesis involves the reaction of cyclic α-ketiminophosphonates with indoles using an H8-BINOL-derived chiral phosphoric acid (CPA) catalyst that bears electron-withdrawing 3,5-ditrifluoromethylphenyl substituents on its 3- and 3'-positions. This Friedel–Crafts reaction of cyclic α-ketiminophosphonates was also successful with pyrrole.

Key words: Friedel–Crafts reaction, Quaternary α-aminophosphonate, Indole, Chiral phosphoric acid

严忠, 高翔, 周永贵. 有机催化吲哚与环状酮亚胺膦酸酯的傅-克反应合成含手性季碳胺基膦酸衍生物[J]. 催化学报, 2017, 38(5): 784-792.

Zhong Yan, Xiang Gao, Yong-Gui Zhou. Enantioselective synthesis of quaternary α-aminophosphonates by organocatalytic Friedel–Crafts reactions of indoles with cyclic α-ketiminophosphonates[J]. Chinese Journal of Catalysis, 2017, 38(5): 784-792.

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