Axially chiral cyclohexylidenes exhibit unique chirality because of the restricted rotation of the C=C bond. Compared with other axially chiral compounds, they are much less explored, and their efficient construction remains a synthetic challenge. Herein, we report the first palladium-catalyzed asymmetric coupling reaction of aryl iodides with 4-substituted cyclohexanol-derived α-diazocarbonyl compounds to give tetrasubstituted cyclohexylidenes in good yields (up to 92%) with excellent enantioselectivities (up to 96% ee) under mild conditions. This protocol provides a general access to axially chiral cyclohexylidenes. The utility of this unique scaffold was demonstrated by the carboxylic acid serving as a useful chiral ligand in transition-metal-catalyzed C–H bond activation, which showed great promise as a new type of olefin ligand.

由于 C=C 键的旋转受限，轴向手性亚环己基表现出独特的手性。与其他轴向手性化合物相比，它们的探索要少得多，而且它们的高效构建仍然是一个合成挑战。在此，我们报道了第一个钯催化的芳基碘化物与 4-取代环己醇衍生的 α-重氮羰基化合物的不对称偶联反应，以良好的收率（高达 92%）和优异的对映选择性（高达 96% ee ）得到四取代的亚环己基。) 在温和的条件下。该协议提供了对轴向手性亚环己基的一般访问。这种独特支架的实用性通过羧酸在过渡金属催化的 C-H 键活化中作为有用的手性配体得到证明，这显示出作为新型烯烃配体的巨大前景。