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  Photocycloaddition reaction of atropisomeric maleimides: mechanism and selectivity

Chang, X.-P., Zheng, Y., Cui, G., Fang, W.-H., & Thiel, W. (2016). Photocycloaddition reaction of atropisomeric maleimides: mechanism and selectivity. Physical Chemistry Chemical Physics, 18(35), 24713-24721. doi:10.1039/C6CP04919B.

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Chang, Xue-Ping1, Author
Zheng, Yiying2, Author              
Cui, Ganglong1, Author
Fang, Wei-Hai1, Author
Thiel, Walter2, Author              
Affiliations:
1Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China , ou_persistent22              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Abstract: We report a density functional study on the mechanism of the [2+2] photocyclization of atropisomeric maleimides. Experimentally, the reaction is known to proceed through the triplet state. We have located all relevant S0 and T1 minima and transition states, as well as the T1/S0 crossing points, and mapped eight stepwise photocyclization pathways for four different conformers in the T1 state that lead to distinct regioisomers. In the preferred four pathways (one for each conformer) the initially formed C–C bond involves the terminal carbon atom of the alkene moiety. This regioselectivity originates from electrostatic preferences (arising from the charge distribution in the polarized C=C double bonds) and from the different thermodynamic stability of the resulting triplet diradical intermediates (caused by electron donation effects that stabilize the radical centers). The formation of the second C–C bond is blocked in the T1 state by prohibitively high barriers and thus occurs after intersystem crossing to the ground state. Furthermore, we rationalize substitution effects on enantioselectivity and diastereoselectivity and identify their origin.

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Language(s): eng - English
 Dates: 2016-07-152016-08-152016-08-162016-09-21
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C6CP04919B
 Degree: -

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 18 (35) Sequence Number: - Start / End Page: 24713 - 24721 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1