Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties

Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties Full article

Journal

Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215

Output data

Year: 2018, Volume: 122, Number: 36, Pages: 7107-7117 Pages count : 11 DOI: 10.1021/acs.jpca.8b05212

Authors

Glebov Evgeni M. ^1,2 , Ruban Natalia V. ^3,2 , Pozdnyakov Ivan P. ^1,2 , Grivin Vjacheslav P. ¹ , Plyusnin Victor F. ^1,2 , Lvov Andrey G. ⁴ , Zakharov Alexey V. ⁴ , Shirinian Valerii Z. ⁴

Affiliations

1	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, 3, Institutskaya Str., Novosibirsk, 630090, Russia
2	Novosibirsk State University, 2, Pirogova str., Novosibirsk, 630090, Russia
3	A. V. Nikolaev Institute of Inorganic Chemistry, 3 Lavrentyev prosp., Novosibirsk, 630090, Russia
4	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47, Leninsky prosp., 119991 Moscow, Russia

Photoinduced rearrangement of diarylethenes to naphthalenes or isoelectronic benzoannulated heterocycles is a novel reaction in preparative organic photochemistry. Recently it was shown that unsymmetrical diarylethenes containing benzene and oxazole derivatives efficiently undergo this transformation leading to amide derivatives of naphthalene. Mechanistic study of skeletal rearrangement for a typical representative of these compounds, namely 3-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one, was performed by stationary and laser flash photolysis as well as density functional theory (DFT) calculations. The mechanism of the rearrangement was found to comprise several thermal stages. Both singlet and triplet states of the initial compound can be transformed to the reaction product, which results in the dependence of the quantum yield vs concentration of dissolved oxygen. Three reactive intermediates were registered in the laser flash photolysis experiment; the predicted structures were in accordance with DFT calculations of the electronic absorption spectra. In addition to the previously proposed mechanism of skeletal rearrangement based on a sigmatropic shift of hydrogen, two new parallel pathways based on formation of a carbanion/carbocation were determined.

Glebov E.M. , Ruban N.V. , Pozdnyakov I.P. , Grivin V.P. , Plyusnin V.F. , Lvov A.G. , Zakharov A.V. , Shirinian V.Z.
Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties
Journal of Physical Chemistry A. 2018. V.122. N36. P.7107-7117. DOI: 10.1021/acs.jpca.8b05212 WOS Scopus Scopus OpenAlex

Web of science:	WOS:000444924000001
Scopus:	2-s2.0-85053001403 \| 2-s2.0-85063338616
OpenAlex:	W2888431899

DB	Citing
OpenAlex	18
Scopus	2 15
Web of science	14