TY - JOUR

T1 - Oxidative Ring-Opening Transformation of 5-Acyl-4-pyrones as an Approach for the Tunable Synthesis of Hydroxylated Pyrones and Furans

AU - Steparuk, Elena

AU - Meshcheryakova, Ekaterina A.

AU - Viktorova, Viktoria

AU - Ulitko, Maria

AU - Obydennov, Dmitrii

AU - Sosnovskikh, Vyacheslav

N1 - This work was financially supported by the Russian Science Foundation (Grant 22-73-10236, https://rscf.ru/project/22-73-10236/ ). Analytical studies were carried out using equipment at the Center for Joint Use ‘Spectroscopy and Analysis of Organic Compounds’ at the Postovsky Institute of Organic Synthesis of the Russian Academy of Sciences (Ural Branch) and the Laboratory of Complex Investigations and Expert Evaluation of Organic Materials of the Center for Joint Use at the Ural Federal University.

PY - 2023

Y1 - 2023

N2 - A selective and tunable approach for oxidation of 4-pyroneshasbeen developed via ring-opening transformations leadingto various hydroxylated oxaheterocycles. The first step of the strategyincludes the base-catalyzed epoxidation of 5-acyl-4-pyrones in thepresence of hydrogen peroxide for the effective synthesis of pyroneepoxides in high yields. The epoxides bearing the CO(2)Etgroup are reactive molecules that can undergo both pyrone and oxiranering-opening via deformylation to produce hydroxylated2-pyrones or 4-pyrones. The acid-promoted transformation led to 3-hydroxy-4-pyrones(24-76% yields), whereas the K2CO3-catalyzedring-opening process of 2-carbethoxy-4-pyrone epoxides proceeded asan attack of alcohol at the C-3 position bearing the CO2Et group to give functionalized 6-acyl-5-hydroxy-2-pyrones (27-87%yields). The base-catalyzed reaction of 2-aryl-4-pyrone epoxides wasfollowed by ring contraction and the dearoylation process to produce3-hydroxyfuran-2-carbaldehydes in 42-80% yields. The transformationof 3-aroylchromone epoxides led to flavonols and 3-hydroxybenzofuran-2-carbaldehydein the acidic and basic conditions, respectively. The prepared hydroxylatedheterocycles demonstrated high reactivity for further transformationsand low cytotoxicity and are promising fluorophores or UV filters.

AB - A selective and tunable approach for oxidation of 4-pyroneshasbeen developed via ring-opening transformations leadingto various hydroxylated oxaheterocycles. The first step of the strategyincludes the base-catalyzed epoxidation of 5-acyl-4-pyrones in thepresence of hydrogen peroxide for the effective synthesis of pyroneepoxides in high yields. The epoxides bearing the CO(2)Etgroup are reactive molecules that can undergo both pyrone and oxiranering-opening via deformylation to produce hydroxylated2-pyrones or 4-pyrones. The acid-promoted transformation led to 3-hydroxy-4-pyrones(24-76% yields), whereas the K2CO3-catalyzedring-opening process of 2-carbethoxy-4-pyrone epoxides proceeded asan attack of alcohol at the C-3 position bearing the CO2Et group to give functionalized 6-acyl-5-hydroxy-2-pyrones (27-87%yields). The base-catalyzed reaction of 2-aryl-4-pyrone epoxides wasfollowed by ring contraction and the dearoylation process to produce3-hydroxyfuran-2-carbaldehydes in 42-80% yields. The transformationof 3-aroylchromone epoxides led to flavonols and 3-hydroxybenzofuran-2-carbaldehydein the acidic and basic conditions, respectively. The prepared hydroxylatedheterocycles demonstrated high reactivity for further transformationsand low cytotoxicity and are promising fluorophores or UV filters.

UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001039599600001

UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85167781966

U2 - 10.1021/acs.joc.3c00907

DO - 10.1021/acs.joc.3c00907

M3 - Article

VL - 88

SP - 11590

EP - 11602

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 16

ER -