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231225s2017 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.24897
|2 doi
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|a pubmed25n0914.xml
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|a (DE-627)NLM274365634
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|a (NLM)28762255
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
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|a Liu, Xiang-Yang
|e verfasserin
|4 aut
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|a Theoretical studies of spin state-specific [2 + 2] and [5 + 2] photocycloaddition reactions of n-(1-penten-5-yl)maleimide
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|c 2017
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
|b c
|2 rdamedia
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|a ƒa Online-Ressource
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|2 rdacarrier
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|a Date Revised 20.11.2019
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a © 2017 Wiley Periodicals, Inc.
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|a N-alkenyl maleimides are found to exhibit spin state-specific chemoselectivities for [2 + 2] and [5 + 2] photocycloadditions; but, reaction mechanism is still unclear. In this work, we have used high-level electronic structure methods (DFT, CASSCF, and CASPT2) to explore [2 + 2] and [5 + 2] photocycloaddition reaction paths of an N-alkenyl maleimide in the S1 and T1 states as well as relevant photophysical processes. It is found that in the S1 state [5 + 2] photocycloaddition reaction is barrierless and thus overwhelmingly dominant; [2 + 2] photocycloaddition reaction is unimportant because of its large barrier. On the contrary, in the T1 state [2 + 2] photocycloaddition reaction is much more favorable than [5 + 2] photocyclo-addition reaction. Mechanistically, both S1 [5 + 2] and T1 [2 + 2] photocycloaddition reactions occur in a stepwise, nonadiabatic means. In the S1 [5 + 2] reaction, the secondary C atom of the ethenyl moiety first attacks the N atom of the maleimide moiety forming an S1 intermediate, which then decays to the S0 state as a result of an S1 → S0 internal conversion. In the T1 [2 + 2] reaction, the terminal C atom of the ethenyl moiety first attacks the C atom of the maleimide moiety, followed by a T1 → S0 intersystem crossing process to the S0 state. In the S0 state, the second CC bond is formed. Our present computational results not only rationalize available experiments but also provide new mechanistic insights. © 2017 Wiley Periodicals, Inc
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a alkenyl maleimides
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|a asymmetric reaction
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|a chemoselectivity
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|a excited states
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| 650 |
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|a photocycloaddition
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| 700 |
1 |
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|a Xiao, Pin
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Fang, Wei-Hai
|e verfasserin
|4 aut
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| 700 |
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|a Cui, Ganglong
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 38(2017), 28 vom: 30. Okt., Seite 2388-2395
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:38
|g year:2017
|g number:28
|g day:30
|g month:10
|g pages:2388-2395
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|u http://dx.doi.org/10.1002/jcc.24897
|3 Volltext
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