Asymmetric Photocatalysis by Intramolecular Hydrogen‐Atom Transfer in Photoexcited Catalyst–Substrate Complex. Issue 41 (30th August 2019)

• Record Type: Journal Article
• Authors: Zhang, Chenhao; Chen, Shuming; Ye, Chen‐Xi; Harms, Klaus; Zhang, Lilu; Houk, K. N.; Meggers, Eric
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 41(2019)
• Page Start: 14462
• Page End: 14466
• Publication Date: 2019-08-30
• Subjects: asymmetric catalysis -- Diels–Alder -- hydrogen atom transfer -- photochemistry -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201905647
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 3‐(2‐Formylphenyl)‐1‐pyrazol‐1‐yl‐propenones undergo an asymmetric photorearrangement to benzo[ d ]cyclopropa[ b ]pyranones with up to >99 % ee, which is catalyzed by a bis‐cyclometalated rhodium catalyst in the presence of visible light. Mechanistic experiments and DFT calculations support a mechanism in which a photoexcited catalyst/substrate complex triggers an intramolecular hydrogen‐atom transfer followed by a highly stereocontrolled hetero‐Diels–Alder reaction. In this reaction scheme, the rhodium catalyst fulfills multiple functions by 1) enabling visible‐light π→π* excitation of the catalyst‐bound enone substrate, 2) facilitating the hydrogen‐atom transfer, and 3) providing the asymmetric induction for the hetero‐Diels–Alder reaction. Abstract : If the hat fits : The depicted catalytic asymmetric photoreaction proceeds through a 1, 5‐hydrogen‐atom transfer (HAT) within a photoexcited catalyst/substrate complex, followed by a highly stereocontrolled hetero‐Diels–Alder reaction. This work expands the reaction modes of photoexcited catalyst/substrate complexes for applications in asymmetric catalysis.