Photochemically Induced Ring Opening of Spirocyclopropyl Oxindoles: Evidence for a Triplet 1,3-Diradical Intermediate and Deracemization by a Chiral Sensitizer.

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.