Chiral polycyclic indolines are widely present in natural products and have become the focus of extensive synthetic efforts. Here, we show the catalytic asymmetric dearomative [3 + 2] annulation of indoles with donor-acceptor aminocyclopropanes to construct tricyclic indolines. Key to the success of the reaction is the rational design of C₁-symmetric bifunctional tridentate imidazoline-pyrroloimidazolone pyridine ligand. Under 5 mol% of Ni(OTf)₂-ligand complex, diverse tricyclic indolines containing cyclopentamine moieties are obtained in good chemoselectivities, high diastereoselectivities, and excellent enantioselectivities. An unusual cis-configuration ligand is superior to the trans-configuration ligand and the corresponding C₂-symmetric tridentate nitrogen ligands in the annulation reaction. Mechanistic studies by control experiments and density functional theory calculations reveal a dual activation manner, where Ni(II) complex activates the aminocyclopropane via coordination with the geminal diester, and imidazolidine NH forms a H-bond with the succinimide moiety.

手性多环二氢吲哚广泛存在于天然产物中，已成为广泛合成努力的焦点。在这里，我们展示了吲哚与供体-受体氨基环丙烷催化不对称脱芳烃 [3 + 2] 环化以构建三环二氢吲哚。反应成功的关键是合理设计C ₁ -对称双功能三齿咪唑啉-吡咯并咪唑酮吡啶配体。在 5 mol% 的 Ni(OTf) ₂ -配体络合物下，以良好的化学选择性、高非对映选择性和优异的对映选择性获得了多种含有环戊胺部分的三环二氢吲哚。一种不寻常的顺式配体优于反式环化反应中的-构型配体和相应的C _{2 -}对称三齿氮配体。通过控制实验和密度泛函理论计算的机理研究揭示了双重激活方式，其中 Ni(II) 配合物通过与孪生二酯配位激活氨基环丙烷，咪唑烷 NH 与琥珀酰亚胺部分形成氢键。