Diverting Ni‐Catalyzed Direct Benzylic C–H Hydroxylation towards Trifluoroethoxylation | Sciact - CRIS-система Института катализа

Diverting Ni‐Catalyzed Direct Benzylic C–H Hydroxylation towards Trifluoroethoxylation Научная публикация

Журнал

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Вых. Данные

Год: 2024, Том: 16, Номер: 7, Номер статьи : e202301346, Страниц : 9 DOI: 10.1002/cctc.202301346

Ключевые слова

Alkoxylation, C–H activation, homogeneous catalysis, nickel, selective oxygenation

Авторы

Bushmin Dmitry S. ¹ , Samsonenko Denis G. ² , Talsi Evgenii P. ¹ , Lyakin Oleg Y. ¹ , Bryliakov Konstantin P. ³

Организации

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, 630090 Novosibirsk (Russia)
2	Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, 630090 Novosibirsk (Russia)
3	Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, 119991 Moscow (Russia)

Информация о финансировании (2)

1	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0001 (121031700321-3)
2	Российский научный фонд	22-13-00225

Nickel(II) complexes with the simple N4 donor aminopyridine ligands BPMEN (N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-diaminoethane) and TPA (tris(2-pyridylmethyl)amine) have been demonstrated to perform as efficient catalysts for the regioselective oxygenation of benzylic C–H groups with m-chloroperoxybenzoic acid under mild conditions (at 20 °C), typically ensuring >90 % substrate conversions within 1 h at 1 mol % catalyst loadings. Unprecedentedly, replacing the commonly used mixed reaction solvent CH3CN/CH2Cl2 with 2,2,2-trifluoroethanol diverts the selectivity of the above Ni-based catalyst systems from hydroxylation/ketonization to trifluoroalkoxylation, with the formation of 1-phenylalkyl 2,2,2-trifluoroethyl ethers. The use of 2,2,2-trifluoroethanol ensures high substrate conversion values (up to 97 %), as well as high selectivity for the ether formation (up to 92 %). Preliminary discussion of the reaction mechanism is given based on the catalytic and literature data.

Bushmin D.S. , Samsonenko D.G. , Talsi E.P. , Lyakin O.Y. , Bryliakov K.P.
Diverting Ni‐Catalyzed Direct Benzylic C–H Hydroxylation towards Trifluoroethoxylation
ChemCatChem. 2024. V.16. N7. e202301346 :1-9. DOI: 10.1002/cctc.202301346 WOS Scopus РИНЦ CAPlus OpenAlex

Поступила в редакцию:	23 окт. 2023 г.
Принята к публикации:	26 нояб. 2023 г.
Опубликована online:	27 нояб. 2023 г.
Опубликована в печати:	8 апр. 2024 г.

Web of science:	WOS:001126771000001
Scopus:	2-s2.0-85179942824
РИНЦ:	62786343
Chemical Abstracts:	2023:2662616
OpenAlex:	W4389069716

БД	Цитирований
OpenAlex	2
Scopus	3
Web of science	3