Base-mediated tandem photochemical rearrangement/ring-opening approach to α-ketoamides from 2-arylallomaltols

Base-mediated tandem photochemical rearrangement/ring-opening approach to α-ketoamides from 2-arylallomaltols Full article

Journal

Organic & Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539

Output data

Year: 2026, DOI: 10.1039/d6ob01429a

Authors

Milyutin Constantine V. ¹ , Komogortsev Andrey N. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Pr., 47, Moscow, 119991, Russian Federation

A concise one-pot synthesis of aroyl-containing α-ketoamides from 2-aryl-substituted allomaltols has been established. The transformation proceeds through a visible light induced anionic photorearrangement to 3-hydroxypyran-2-one intermediates, which undergo in situ secondary amine-promoted ring opening. The employed secondary amines play a dual role, serving both as bases for the generation of photoactive anions and as nucleophiles for the subsequent ring-opening step. This newly developed tandem strategy enables efficient access to a series of α-ketoamides from readily available allomaltol derivatives in yields of up to 87%. Notably, irradiation of the same substrates in the absence of base follows an alternative ESIPT-induced pyranone ring contraction pathway, generating unstable α-hydroxy-1,2-diketones that were trapped in situ with o-phenylenediamine to afford quinoxaline derivatives

Milyutin C.V. , Komogortsev A.N.
Base-mediated tandem photochemical rearrangement/ring-opening approach to α-ketoamides from 2-arylallomaltols
Organic & Biomolecular Chemistry. 2026. DOI: 10.1039/d6ob01429a WOS Scopus OpenAlex

Submitted:	Sep 16, 2026
Accepted:	Oct 20, 2026
Published online:	Oct 26, 2026

≡ Web of science:	WOS:001912424600001
≡ Scopus:	2-s2.0-105054773365
≡ OpenAlex:	W7223692055