Mn-Catalyzed Regio- and Stereoselective C(sp3)–H Lactonization of Carboxylic Acids with H2O2 | Sciact - CRIS-система Института катализа

Mn-Catalyzed Regio- and Stereoselective C(sp3)–H Lactonization of Carboxylic Acids with H2O2 Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2025, Том: 15, Номер: 17, Страницы: 14938-14954 Страниц : 17 DOI: 10.1021/acscatal.5c03762

Ключевые слова

asymmetric catalysis, C−H activation, hydrogen peroxide, lactonization, manganese

Авторы

Kurganskiy Vladimir I. ^1,2 , Bryliakova Anna A. ² , Medvedev Alexander G. ³ , Shashkov Mikhail V. ^1,4 , Bryliakov Konstantin P. ²

Организации

1	Boreskov Institute of Catalysis SB RAS, Lavrentieva 5, Novosibirsk 630090, Russia
2	Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, Moscow 119991, Russia
3	Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky Pr. 31, Moscow 119991, Russia
4	Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Pr. Lavrentieva 9, Novosibirsk 630090, Russia

Информация о финансировании (2)

1	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUR-2024-0032
2	Российский научный фонд	25-13-00108 (125071708733-8)

Recently, nonheme manganese complexes with bis-amino-bis-pyridylmethyl and structurally related ligands have been reported to efficiently catalyze the intramolecular C–H acyloxylation of readily available linear carboxylic (fatty) acids, directly converting those to lactones. Herein, we present the general oxidation protocol, employing H2O2 as the terminal oxidant, which allows deliberately switching the reaction selectivity between γ-lactonization, δ-lactonization, or ω-1 hydroxylation of the fatty acid in synthetically useful yields. γ-Lactonization of carboxylic acids with a linear main chain has been found to proceed enantioselectively in up to 67% ee; in addition, the activation of primary C–H sites can be efficiently performed, to yield γ-butyrolactones in up to 86% yield. The molecular mechanisms responsible for the observed γ-regioselectivity are discussed on the basis of combined experimental (reaction outcome and isotopic labeling) and quantum-chemical (DFT, DLPNO–CCSD(T)) data. The overall picture is formally consistent with the intramolecular 1,7-H abstraction at the triplet potential energy surface, followed by spin crossing to the lower-lying quintet PES, to end up with intramolecular carboxylate rebound.

Kurganskiy V.I. , Bryliakova A.A. , Medvedev A.G. , Shashkov M.V. , Bryliakov K.P.
Mn-Catalyzed Regio- and Stereoselective C(sp3)–H Lactonization of Carboxylic Acids with H2O2
ACS Catalysis. 2025. V.15. N17. P.14938-14954. DOI: 10.1021/acscatal.5c03762 WOS CAPlus OpenAlex

Поступила в редакцию:	2 июн. 2025 г.
Принята к публикации:	8 авг. 2025 г.
Опубликована online:	12 авг. 2025 г.
Опубликована в печати:	5 сент. 2025 г.

Web of science:	WOS:001549368300001
Chemical Abstracts:	2025:2014513
OpenAlex:	W4413174640

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