Light-Induced Reactions of Diazotetrahydrofuranone without Elimination of Nitrogen: Experimental and Mechanistic Study

The energies and lifetimes of the excited states (S1, S2, S5, T1) of a diazotetrahydrofuranone were determined using experimental and computational methods. It was shown that direction of the diazoketone photochemical transformations without elimination of nitrogen is determined by multiplicity and...

Full description

Saved in:
Bibliographic Details
Published inJournal of organic chemistry Vol. 82; no. 21; pp. 11399 - 11405
Main Authors Rodina, Liudmila L, Baranovskii, Victor I, Galkina, Olesia S, Nikolaev, Valerij A, Tonogina, Nina L, Povolotskiy, Alexey V
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 03.11.2017
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
DIAZIRINES
THERMOLYSIS
KETONES
WOLFF REARRANGEMENT
ISOMERIZATION
CHEMISTRY
WAVELENGTH-DEPENDENT PHOTOCHEMISTRY
PHOTOLYSIS
DIAZO MELDRUMS ACID
DIAZOCARBONYL COMPOUNDS
Online AccessGet full text

Cover

More Information
Summary:The energies and lifetimes of the excited states (S1, S2, S5, T1) of a diazotetrahydrofuranone were determined using experimental and computational methods. It was shown that direction of the diazoketone photochemical transformations without elimination of nitrogen is determined by multiplicity and energy of the excited state, generated by UV irradiation of diazo compound: isomerization to α-ketodiazirine proceeds from the singlet S1 state, whereas the alternative process of C–H insertion with hydrazone formation occurs through the triplet T1 state. The most probable excited state that leads to elimination of nitrogen and Wolff rearrangement is one of the highest singlet excited states of diazotetrahydrofuranone.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.7b01848