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

Liudmila L Rodina; Victor I Baranovskii; Olesia S Galkina; Valerij A Nikolaev; Nina L Tonogina; Alexey V Povolotskiy

doi:10.1021/acs.joc.7b01848

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

J Org Chem. 2017 Nov 3;82(21):11399-11405. doi: 10.1021/acs.joc.7b01848.

Authors

Liudmila L Rodina¹, Victor I Baranovskii¹, Olesia S Galkina¹, Valerij A Nikolaev¹, Nina L Tonogina¹, Alexey V Povolotskiy¹

Affiliation

¹ Institute of Chemistry, Saint-Petersburg State University , Universitetskii prospect 26, St. Petersburg, Petergof 198504, Russia.

PMID: 29020449
DOI: 10.1021/acs.joc.7b01848

Abstract

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.