Selective Oxidative Coupling of 3H‐Pyrazol‐3‐ones, Isoxazol‐5(2H)‐ones, Pyrazolidine‐3,5‐diones, and Barbituric Acids with Malonyl Peroxides: An Effective C‐O Functionalization

Selective Oxidative Coupling of 3H‐Pyrazol‐3‐ones, Isoxazol‐5(2H)‐ones, Pyrazolidine‐3,5‐diones, and Barbituric Acids with Malonyl Peroxides: An Effective C‐O Functionalization Full article

Journal

ChemistrySelect
ISSN: 2365-6549

Output data

Year: 2017, Volume: 2, Number: 11, Pages: 3334-3341 Pages count : 8 DOI: 10.1002/slct.201700720

Authors

Terent'ev Alexander O. ^1,2,3 , Vil Vera A. ^1,2,3 , Gorlov Evgenii S. ^2,3 , Rusina Olga N. ^2,3 , Korlyukov Alexander A. ^4,5 , Nikishin Gennady I. ³ , Adam Waldemar ⁶

Affiliations

1	All-Russian Research Institute for Phytopathology, B. Vyazyomy, Moscow Region, 143050 Russian Federation
2	D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya square, Moscow, 125047 Russian Federation
3	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, Moscow, 119991 Russian Federation
4	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova ul, Moscow, 119991 Russian Federation
5	Pirogov Russian National Research Medical University, Ostrovitianov str. 1, Moscow, 117997 Russian Federation
6	Department of Chemistry, Faculty of Natural Sciences, University of Puerto Rico, Rio Piedras, Puerto Rico, 00931 USA

Oxidative functionalization of 3H-pyrazol-3-ones, isoxazol-5(2H)-ones, pyrazolidine-3,5-diones, and barbituric acids by malonyl peroxides results exclusively in C−O coupling products. Traditional hydroxylation, formation of carbonyl groups, or oxidative destruction of the heterocyclic ring are not observed. Under optimized reactions conditions – fluorinated alcohols as activating medium and at room temperature (20 – 25 °C) – the selective C−O coupling proceeds in high yields (up to 94 %). The oxidative insertion into the enolizable C−H bond of the substrate is mechanistically viewed as a nucleophilic attack by the heterocycle onto the electrophilically activated malonyl peroxides. For heterocyclic substrates with an active methylene group - 3H-pyrazol-3-ones, isoxazol-5(2H)-ones, and barbituric acids - both C−H bonds are oxidized to afford double oxidative C−O coupling products in good yields (up to 72 %).

Terent'ev A.O. , Vil V.A. , Gorlov E.S. , Rusina O.N. , Korlyukov A.A. , Nikishin G.I. , Adam W.
Selective Oxidative Coupling of 3H‐Pyrazol‐3‐ones, Isoxazol‐5(2H)‐ones, Pyrazolidine‐3,5‐diones, and Barbituric Acids with Malonyl Peroxides: An Effective C‐O Functionalization
ChemistrySelect. 2017. V.2. N11. P.3334-3341. DOI: 10.1002/slct.201700720 WOS Scopus OpenAlex

≡ Web of science:	WOS:000423913400001
≡ Scopus:	2-s2.0-85030099600
≡ OpenAlex:	W2607347859