常压CO_2促进的铜催化炔丙醇水解制α-羟基酮（英文）
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摘要
α-羟基酮是一类非常有用的结构,广泛存在于各种具有生物活性的合成药物和天然产物中.水对炔丙醇的区域选择性加成为合成α-羟基酮提供了一种简单并且直接的方法.然而,目前已经报道的多种用于炔烃水解的方法对于炔丙醇的适用性较差,这是由于羟基的引入降低了炔烃的活性以及炔丙醇易发生Meyer-Schuster重排和Rupe重排等副反应.另一方面,CO_2可以作为助催化剂促进炔丙醇水解生成α-羟基酮.具体来讲,炔丙醇与CO_2可以发生羧化环化反应得到α-亚烷基环状碳酸酯,亲核性的水与原位产生的α-亚烷基环状碳酸酯反应使其开环,经历脱羧、异构化过程,最终得到α-羟基酮.与炔丙醇的直接水解相比,以CO_2为促进剂可以更加高效、高选择性地得到α-羟基酮.然而,目前发展的用于CO_2促进的炔丙醇水解合成α-羟基酮的反应中,高压的CO_2和过量的碱是不可缺少的.本文发展了廉价且高效的铜催化体系用于CO_2助催化的炔丙醇水解生成α-羟基酮的反应.该催化体系可以在不需要过量碱的存在下使得炔丙醇的水解反应在常压CO_2条件下顺利进行.控制实验结果表明,铜催化炔丙醇和CO_2的羧化环化反应可以在常压CO_2条件下进行,而有机碱可以有效促进α-亚烷基环状碳酸酯与水反应生成α-羟基酮,这解释了我们发展的铜催化体系在常压CO_2条件下高效进行的原因.相同条件下,本文发展的铜催化体系的催化活性明显高于之前报道的银催化剂,凸显了该催化体系的高效性.在最优反应条件下,一系列具有不同烷基或芳基取代基的炔丙醇都表现出良好的反应活性,能以70%–97%的收率转化为相应的α-羟基酮.在合成应用方面,该方法可应用于克级规模实验,反应能以70%的收率得到相应的α-羟基酮产物;而且,该方法也可以应用于口服药物炔孕酮的进一步衍生化.通过逻辑实验以及对核磁谱图的分析,我们还对该反应提出了一个可能的反应机理.总之,我们使用廉价的过渡金属铜催化剂,成功实现了炔丙醇在常压CO_2为助催化剂条件下发生水解反应合成α-羟基酮.该催化体系反应条件温和,底物适用性良好,催化效率高,为合成α-羟基酮提供了一种简单、高效的新方法.
Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO_2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO_2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO_2 as a crucial cocatalyst under mild conditions.
Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO_2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO_2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO_2 as a crucial cocatalyst under mild conditions.
引文
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