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- W4232846428 abstract "Abstract 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." @default.
- W4232846428 created "2022-05-12" @default.
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- W4232846428 creator A5054617760 @default.
- W4232846428 creator A5072124977 @default.
- W4232846428 creator A5083424283 @default.
- W4232846428 date "2020-03-20" @default.
- W4232846428 modified "2023-10-18" @default.
- W4232846428 title "Visible‐Light Photocatalysis of Asymmetric [2+2] Cycloaddition in Cage‐Confined Nanospace Merging Chirality with Triplet‐State Photosensitization" @default.
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- W4232846428 doi "https://doi.org/10.1002/ange.201916722" @default.
- W4232846428 hasPublicationYear "2020" @default.
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