In:
Nature Communications, Springer Science and Business Media LLC, Vol. 14, No. 1 ( 2023-04-20)
Kurzfassung:
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 C 1 -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 C 2 -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.
Materialart:
Online-Ressource
ISSN:
2041-1723
DOI:
10.1038/s41467-023-38059-7
Sprache:
Englisch
Verlag:
Springer Science and Business Media LLC
Publikationsdatum:
2023
ZDB Id:
2553671-0
