[6π] Photocyclization to cis-Hexahydrocarbazol-4-ones: Substrate Modification, Mechanism, and Scope | Zendy

Sachin G. Modha | Zendy; Alexander Pöthig | Zendy; Andreas Dreuw | Zendy; Thorsten Bach | Zendy

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[6π] Photocyclization to cis-Hexahydrocarbazol-4-ones: Substrate Modification, Mechanism, and Scope

Author(s) -

Sachin G. Modha,

Alexander Pöthig,

Andreas Dreuw,

Thorsten Bach

Publication year - 2019

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/acs.joc.8b03144

Subject(s) - conrotatory and disrotatory , alkyl , aryl , chemistry , ring (chemistry) , substrate (aquarium) , quenching (fluorescence) , nitrogen atom , photochemistry , yield (engineering) , acceptor , stereochemistry , materials science , organic chemistry , fluorescence , oceanography , physics , quantum mechanics , metallurgy , geology , condensed matter physics

Upon irradiation at λ = 366 nm, tertiary N-alkoxycarbonyl- N-aryl-β-enaminones furnished exclusively the trans-hexahydrocarbazol-4-ones by a conrotatory [6π] photocyclization but epimerized on silica to cis-hexahydrocarbazol-4-ones (14 examples, 44-98% yield). The acceptor substitution on the nitrogen atom enhanced the stability of the cyclized products compared to N-alkyl- N-aryl-β-enaminones reported previously. The mechanism of the [6π] photocyclization was investigated by quenching experiments, deuterium-labeling experiments, and DFT calculations, suggesting a triplet pathway for the conrotatory ring closure followed by a suprafacial [1,4] hydrogen migration.

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