铜催化偕二硼酸酯的不对称加成反应

Transition-metal catalyzed asymmetric reactions of bis(boronates) or germinal bis(boronates) have been ranked as one of the hot-topic in last decade. Consequently, many strategies have been developed in this area. However, regarding their asymmetric protocols, in terms of high efficiency and wide-scope diversities, less catalytic asymmetric version of the reactions have been reported so far as best of our knowledge. In continuous interests to our previous research, we plan to explore Cu-catalyzed asymmetric reactions with bis(boronates) and germinal bis(boronates), mainly focusing on the following three aspects: achieving the high efficiency of these catalytic system, including creating more chiral centers in one step and meanwhile offering the highly functionalized products; exploring the innovative reaction pattern; and expanding the application of the found efficient methodologies in the synthesis of chiral drugs and active pharmaceutical ingredients, and thus realizing the deep exploration on the concept and application level.

过渡金属催化的联硼酸酯或偕二硼酸酯不对称反应研究是国际上一个难啃的热点。虽然国内也有一些课题组开展了这方面的研究，但总体上来说，高效不对称催化的例子较少，催化效率不是很高，反应类型也有待拓展。因此，本课题将在铜催化不对称硼化反应的基础上，探索实现铜催化联硼酸酯或偕二硼酸酯的不对称加成反应，着力解决以下三方面的问题：1) 金属铜催化联硼酸酯或偕二硼酸酯加成体系的高效性，一步建立多个手性中心，产物含有多个可进一步转化的官能团；2) 探索具有创新性的反应类型；3) 拓展高效方法学在手性药物及药物中间体的合成实例，从概念和应用层面实现深入探索。

过渡金属催化的烯/炔类化合物双官能团化反应作为一种能够快速高效引入多官能团的重要方法，在有机合成中得到了广泛应用，也为构建化学结构的多样性提供了有力的手段。本项目中，我们基于过渡金属催化的环己二烯酮的 1,6-双官能化反应，在1,6-烯联烯的不对称硼化环化反应的基础上，发展了含有环己二烯酮的 1,6-烯炔、1,6-烯联烯和 1,6-二烯三种类型底物的催化串联反应的方法学，为顺式的氢化苯并呋喃、 氢化吲哚以及氢化茚提供了高效的合成方法。产物可以进一步地转化为其他结构，具有很高的合成应用价值。通过催化机理的深入研究，揭示了其区域选择性和立体选择性的调控机制，为该类底物将来的反应设计提供了良好的基础。

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