Development of Organoallylation Reagent and Asymmetric Organocatalysis

环境友好转化的发展是有机合成的重要课题之一。尽管不对称有机催化已被公认为能够有效地服务于光学活性化合物的方法之一，但其适用性和通用性仍然受到限制。在本研究中，我们基于有机烯丙化试剂的设计，开发了不对称重排反应。我们发现，Brnsted酸促进了高烯丙基胺或高烯丙基亚胺的1，3-重排反应，从而以良好的手性转移比提供光学活性的4，4-取代高烯丙基胺。据我们所知，这是第一个不对称1，3-重排合成高烯丙基胺的例子。

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.