Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation Full article

Journal

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

Output data

Year: 2024, Volume: 16, Number: 7, Article number : e202301346, Pages count : DOI: 10.1002/cctc.202301346

Authors

Bushmin Dmitry ¹ , Samsonenko Denis ² , Talsi Evgenii ¹ , Lyakin Oleg ¹ , Bryliakov Konstantin Petrovich ³

Affiliations

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

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. , Samsonenko D. , Talsi E. , Lyakin O. , Bryliakov K.P.
Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation
ChemCatChem. 2024. V.16. N7. e202301346 . DOI: 10.1002/cctc.202301346 WOS Scopus OpenAlex

Web of science:	WOS:001126771000001
Scopus:	2-s2.0-85179942824
OpenAlex:	W4389069716

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OpenAlex	7
Scopus	7
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