Development of Organoallylation Reagent and Asymmetric Organocatalysis

发展环境良性转化是有机合成领域的重要课题之一。虽然不对称有机催化已被公认为是有效服务于光活性化合物的有机催化方法之一，但其适用性和通用性仍然有限。在本研究中，我们基于有机烯丙基化试剂的设计，建立了不对称重排反应。研究发现，Brønsted酸能促进同丙烯胺或同丙烯胺的1,3重排反应，以优异的手性转移率提供具有光学活性的4,4取代同丙烯胺。据我们所知，这是合成全烯丙胺的不对称1,3重排的第一个例子。

The development of environmentally benign transformation is one of the most important subjects in organic synthesis. Although asymmetric organocatalysis has been recognized as one of them to serve optically active compounds efficiently, there has been still limited in the applicability and generality. In the present study, we developed asymmetric rearrangement reaction based on the design of organo allylation reagents. We found that Brønsted acid promoted 1,3-rearrangement reaction of homoallyl amines or homoallylic imines to serve optically active 4,4-substituted homoallyl amines in excellent chirality transfer ratio. To the best our knowledge, this is the first example of the asymmetric 1,3-rearragement for homoallyl amines synthesis.