华东理工大学Yifeng Chen研究团队取得一项新突破。他们开发出未活化烯烃的催化去对称二碳官能化。这一研究成果发表在2022年3月14日出版的国际学术期刊《德国应用化学》上。

在该研究中，课题组通过镍催化的还原交叉偶联反应，揭示了一种前所未有的1,6-二烯的去对称二碳官能化反应。利用未开发的手性8-Quinox可以使未激活的单取代和双取代烯烃在镍催化下发生去对称氨基甲酰烷基化反应，以高对映性和立体选择性生成含两个不连续的立体中心的吡咯烷酮，且该反应具有宽广的官能团兼容性。吡咯烷酮的合成应用使人们能够快速获得复杂的手性并环杂环化合物。

据介绍，过渡金属催化交叉偶联反应构建多立体中心是一个棘手的挑战。与此同时，未活化烯烃的催化去对称官能化很大程度上还有待探索。

附：英文原文

Title: Catalytic Desymmetric Dicarbofunctionalization of Unactivated Alkenes

Author: Xianqing Wu, Baixue Luan, Wenyu Zhao, Feng He, Xin-Yan Wu, Jingping Qu, Yifeng Chen

Issue&Volume: 2022-03-14

Abstract: The construction of multi-stereocenters of transition metal-catalyzed cross-coupling reaction is a stubborn challenge. In the meanwhile, catalytic desymmetric functionalization of unactivated alkene remains largely unexplored. Herein, we disclose an unprecedented desymmetric dicarbofunctionalization of 1,6-dienes  via  nickel-catalyzed reductive cross-coupling reaction. The leverage of underdeveloped chiral 8-Quinox enables Ni-catalyzed desymmetric carbamoylalkylation of both unactivated mono- and disubstituted alkenes to forge the pyrrolidinone bearing two uncontinuous stereogenic centers in high enantio- and stereoselectivitives with broad functional group tolerance. The synthetic application of pyrrolidinones allows the rapid access to the complex chiral fused-heterocycles.

DOI: 10.1002/anie.202111598

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202111598