Premium
Photochemically Induced Ring Opening of Spirocyclopropyl Oxindoles: Evidence for a Triplet 1,3‐Diradical Intermediate and Deracemization by a Chiral Sensitizer
Author(s) -
Li Xinyao,
Kutta Roger J.,
Jandl Christian,
Bauer Andreas,
Nuernberger Patrick,
Bach Thorsten
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202008384
Subject(s) - diradical , thioxanthone , chemistry , photochemistry , cyclopropene , enantiomer , cyclopropane , photosensitizer , ring (chemistry) , stereochemistry , medicinal chemistry , organic chemistry , polymerization , physics , nuclear physics , singlet state , excited state , photopolymer , polymer
Abstract The photochemical deracemization of spiro[cyclopropane‐1,3′‐indolin]‐2′‐ones (spirocyclopropyl oxindoles) was studied. The corresponding 2,2‐dichloro compound is configurationally labile upon direct irradiation at λ =350 nm and upon irradiation at λ =405 nm in the presence of achiral thioxanthen‐9‐one as the sensitizer. The triplet 1,3‐diradical intermediate generated in the latter reaction was detected by transient absorption spectroscopy and its lifetime determined ( τ =22 μs). Using a chiral thioxanthone or xanthone, with a lactam hydrogen bonding site as a photosensitizer, allowed the deracemization of differently substituted chiral spirocyclopropyl oxindoles with yields of 65–98 % and in 50–85 % ee (17 examples). Three mechanistic contributions were identified to co‐act favorably for high enantioselectivity: the difference in binding constants to the chiral thioxanthone, the smaller molecular distance in the complex of the minor enantiomer, and the lifetime of the intermediate 1,3‐diradical.