We report the first Rh₂(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetra-hydropyridines in good yields and excellent enantioselectivities under mild conditions. The activated group, CHZ (Z is electron-withdrawing group (EWG)), in the enyne substrates exerts two synergetic roles, one is to activate alkyne for the cyclopropanation reaction; the other is to introduce the C-H···O interaction between substrate and catalyst (reducing the energy barrier of the reaction). This double-mode activation was supported by both density functional theory (DFT) calculations and experimental tests. This strategy was also extended to other CH₂Z (Z can be OH, OMe, F) as activating groups that made the CH₂ more acidic so that the substrates could also form increased C-H···O interaction with the catalyst.

我们报道了第一个Rh ₂（II）催化的活化的炔烃的不对称环异构化，以在温和的条件下以良好的收率和优异的对映选择性提供环丙烷融合的四氢吡啶。烯基中的活化基团CHZ（Z为吸电子基团（EWG））发挥两种协同作用，一种是活化炔烃以进行环丙烷化反应；另一种是活化炔基。另一种是在底物和催化剂之间引入CH··O相互作用（减少反应的能垒）。密度泛函理论（DFT）计算和实验测试均支持这种双模激活。此策略还扩展到其他CH ₂ Z（Z可以是OH，OMe，F）作为形成CH _2的活化基团 酸性更高，因此底物还可以与催化剂形成更多的CH···O相互作用。