Diastereodivergent heterocycle synthesis has been recognized as an important tool for drug discovery in recent years, yet strategies based on nickelacycle formation have not been established. Here, we report a NHC-Ni catalyzed highly 1,3- and 1,4-diastereodivergent heterocycle synthesis from enyne, which is achieved by manipulating the enyne N-substituent (allowing switching of selectivity from up to 2:98 to 98:2). The key to success is the efficient diastereodivergent formation of a nickelacyclopentene, with broad enyne scope at mild conditions, which subsequently provides reductive hydroalkenylation, acylation and silylation products on demand. Diastereoisomers which are sterically hard to distinguish or difficult to access by conventional routes are now accessible easily, including those with very similar 4°, contiguous and skipped stereocenters.

近年来，非对映杂环合成已被公认为药物发现的重要工具，但尚未建立基于镍环形成的策略。在这里，我们报告了 NHC-Ni 催化高度 1,3- 和 1,4- 非对映异杂环从烯炔合成，这是通过操纵烯炔 N- 取代基实现的（允许将选择性从高达 2:98 切换到 98:2 ). 成功的关键是镍环戊烯的有效非对映体形成，在温和条件下具有广泛的烯炔范围，随后可根据需要提供还原性加氢烯基化、酰化和甲硅烷基化产物。空间上难以区分或难以通过常规途径获得的非对映异构体现在很容易获得，包括那些具有非常相似的 4°，