武汉大学化学与分子科学学院Wen-Bo Liu课题组在最新研究中，提出了镍催化炔对映选择性双官能化合成含季中心和无保护亚胺的奥卡西平衍生物。该研究于2023年12月26日发表于国际一流学术期刊《中国化学》上。

在这项研究中，该课题组提出了Ni(II)催化的炔的不对称双官能化，包括分子间区域选择性芳基化和分子内腈加成，从而合成了对映富集的氮卓衍生物。该反应同时建立了一个全碳的季立体中心，并引入了一个无保护的亚胺官能团，为后续转化显示了很大的希望。

该反应对各种官能团都有良好的耐受性，产率高，对映选择性强。通过克级合成和产品衍生化进一步证明了这种方法的合成效用。本研究为合成七元氮杂环提供了另一种方法。

研究人员表示，氮卓环是具有重要生物学意义的分子的重要结构支架。

附：英文原文

Title: Ni-Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine

Author: Jian Long, Zhiwu Lu, Xiao-Lin Li, Peng Xue, Wen-Bo Liu

Issue&Volume: 2023-12-26

Abstract: The azepine ring is a prominent structural scaffold in biologically significant molecules. In this study, we present a Ni(II)-catalyzed asymmetric difunctionalization of alkynes, involving intermolecular regioselective arylation and intramolecular nitrile addition, enabling the synthesis of enantioenriched azepine derivatives. This reaction simultaneously establishes an all-carbon quaternary stereocenter and introduces an unprotected imine functionality, showing great promise for subsequent transformations. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities. The synthetic utility of this methodology is further demonstrated through gram-scale synthesis and product derivatization. This research offers an alternative approach to the synthesis of seven-membered nitrogen heterocycles.

DOI: 10.1002/cjoc.202300647

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.202300647