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Visible‐Light Photocatalysis of Asymmetric [2+2] Cycloaddition in Cage‐Confined Nanospace Merging Chirality with Triplet‐State Photosensitization
Author(s) -
Guo Jing,
Fan YanZhong,
Lu YuLin,
Zheng ShaoPing,
Su ChengYong
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.201916722
Subject(s) - cycloaddition , enantioselective synthesis , photocatalysis , supramolecular chemistry , chemistry , chirality (physics) , photochemistry , supramolecular chirality , catalysis , axial chirality , stereochemistry , crystallography , organic chemistry , crystal structure , physics , quantum mechanics , quark , nambu–jona lasinio model , chiral symmetry breaking
Although the photodimerization of acenaphthylene (ACE) has been known for 100 years, the asymmetric cycloaddition of its 1‐substituted derivatives is unknown. Herein, we report a supramolecular photochirogenic approach in which a homochiral and photoactive Δ / Λ ‐[Pd 6 (RuL 3 ) 8 ] 28+ metal–organic cage ( Δ / Λ ‐MOC‐16) is used as a supramolecular reactor for the enantioselective exited‐state photocatalysis of 1‐Br‐ACE. Owing to preorganization of the substrates by the supramolecular cage, stereochemical control of the triplet state, and nanospace transfer of energy and chirality, the cycloaddition of ACE proceeded with high selectivity for the formation of anti over syn stereoisomers, whereas the regio‐, stereo‐, and enantioselective cycloaddition of unsymmetrical 1‐Br‐ACE showed effective enantiodifferentiation of a pair of anti head‐to‐head stereoisomers. The enzyme‐mimicking photocatalysis was verified by catalytic turnover, rate enhancement, and competing‐guest inhibition experiments.