TY - JOUR

T1 - Palladium catalyzed C(sp3)–H trifluoroethoxylation

AU - Lubov, Dmitry P.

AU - Ivanov, Konstantin S.

AU - Nefedov, Andrey A.

AU - Talsi, Evgenii P.

AU - Bryliakov, Konstantin P.

N1 - The authors thank the Ministry of Science and Higher Education of the Russian Federation for the financial support of this work (synthetic and catalytic studies), project FWUR-2024-0032 for Boreskov Institute of Catalysis. AAN is grateful to the Ministry of Science and Higher Education, project for Vorozhtsov Novosibirsk Institute of Organic Chemistry (HR-MS measurements). KSI is grateful to the Ministry of Science and Higher Education of the Russian Federation (NMR and GC-MS analyses).

PY - 2024

Y1 - 2024

N2 - Palladium(II) complexes of the TPA family (TPA − tris(2-pyridylmethyl)amine) have recently emerged as efficient catalysts of highly 3°-regioselective hydroxylation and chemoselective 2°-ketonization of aliphatic C–H groups with peroxycarboxylic acids. Herewith, we present a novel facet of the catalytic reactivity of such complexes that have been shown to mediate highly efficient (at as low as 0.6 mol. % catalyst loadings) and selective trifluoroethoxylation of organic substrates at benzylic C–H groups, affording the corresponding trifluoroethoxy ethers in up to 73 % isolated yield. The developed synthetic protocol allows for diastereoselective trifluoroethoxylation of complex molecules of natural origin (steroids, terpenoids).

AB - Palladium(II) complexes of the TPA family (TPA − tris(2-pyridylmethyl)amine) have recently emerged as efficient catalysts of highly 3°-regioselective hydroxylation and chemoselective 2°-ketonization of aliphatic C–H groups with peroxycarboxylic acids. Herewith, we present a novel facet of the catalytic reactivity of such complexes that have been shown to mediate highly efficient (at as low as 0.6 mol. % catalyst loadings) and selective trifluoroethoxylation of organic substrates at benzylic C–H groups, affording the corresponding trifluoroethoxy ethers in up to 73 % isolated yield. The developed synthetic protocol allows for diastereoselective trifluoroethoxylation of complex molecules of natural origin (steroids, terpenoids).

KW - Alkoxylation

KW - Alternative rebound

KW - C–H activation

KW - Heterofunctionalization

KW - Palladium

KW - Selective oxidation

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85194074356&origin=inward&txGid=590f7a7900888f8287bfd057a4a82817

UR - https://www.mendeley.com/catalogue/e6af6f99-a711-34fa-9b54-4ab7cd136d64/

U2 - 10.1016/j.jcat.2024.115563

DO - 10.1016/j.jcat.2024.115563

M3 - Article

VL - 435

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

M1 - 115563

ER -