Diverting Ni‐Catalyzed Direct Benzylic C–H Hydroxylation towards Trifluoroethoxylation Full article
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ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899 |
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| Output data | Year: 2024, Volume: 16, Number: 7, Article number : e202301346, Pages count : 9 DOI: 10.1002/cctc.202301346 | ||||||
| Tags | Alkoxylation, C–H activation, homogeneous catalysis, nickel, selective oxygenation | ||||||
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| Affiliations |
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Funding (2)
| 1 | Ministry of Science and Higher Education of the Russian Federation | FWUZ-2021-0001 (121031700321-3) |
| 2 | Russian Science Foundation | 22-13-00225 |
Abstract:
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.
Cite:
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 AN OpenAlex
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 AN OpenAlex
Dates:
| Submitted: | Oct 23, 2023 |
| Accepted: | Nov 26, 2023 |
| Published online: | Nov 27, 2023 |
| Published print: | Apr 8, 2024 |
Identifiers:
| Web of science: | WOS:001126771000001 |
| Scopus: | 2-s2.0-85179942824 |
| Elibrary: | 62786343 |
| Chemical Abstracts: | 2023:2662616 |
| OpenAlex: | W4389069716 |