TY - JOUR

T1 - One-Pot Myrtenol Amination over Au, Au–Pd and Pd Nanoparticles Supported on Alumina

AU - Demidova, Yu S.

AU - Simakova, I. L.

AU - Estrada, M.

AU - Beloshapkin, S.

AU - Suslov, E. V.

AU - Volcho, K. P.

AU - Salakhutdinov, N. F.

AU - Simakov, A.

AU - Murzin, D. Yu

PY - 2019/12/1

Y1 - 2019/12/1

N2 - One-pot bio-based myrtenol amination was studied in the presence of alumina supported Au, Au–Pd and Pd nanoparticles subjected to the thermal treatment under oxidizing or reducing atmosphere. Myrtenol amination with aniline was carried out under nitrogen atmosphere (9 bar) at 453 K using toluene as a solvent. The effect of the active metal along with the influence of redox pre-treatment on the catalytic behavior in the hydrogen borrowing reaction was explored. The catalyst characterization was done by transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, nitrogen adsorption. The active metal and the catalysts redox pretreatment affected more noticeably selectivity to the reaction products rather than myrtenol conversion. Monometallic Au/Al2O3 catalyst promoted predominantly formation of the target secondary amine and the corresponding imine without a significant impact of the side reaction of C=C bond hydrogenation in myrtenol, whereas monometallic Pd catalyst activated C=C bond resulting in its hydrogenation. At the same time in the presence of Au–Pd simultaneous hydrogenation of both C=C and C=N bond occurred. Au–Pd catalysts activated in oxygen and hydrogen showed different catalytic activity determined by the composition of surface active sites. Monometallic gold catalyst was more effective in the hydrogen transfer in the case of substrates with competitive unsaturated functional groups.

AB - One-pot bio-based myrtenol amination was studied in the presence of alumina supported Au, Au–Pd and Pd nanoparticles subjected to the thermal treatment under oxidizing or reducing atmosphere. Myrtenol amination with aniline was carried out under nitrogen atmosphere (9 bar) at 453 K using toluene as a solvent. The effect of the active metal along with the influence of redox pre-treatment on the catalytic behavior in the hydrogen borrowing reaction was explored. The catalyst characterization was done by transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, nitrogen adsorption. The active metal and the catalysts redox pretreatment affected more noticeably selectivity to the reaction products rather than myrtenol conversion. Monometallic Au/Al2O3 catalyst promoted predominantly formation of the target secondary amine and the corresponding imine without a significant impact of the side reaction of C=C bond hydrogenation in myrtenol, whereas monometallic Pd catalyst activated C=C bond resulting in its hydrogenation. At the same time in the presence of Au–Pd simultaneous hydrogenation of both C=C and C=N bond occurred. Au–Pd catalysts activated in oxygen and hydrogen showed different catalytic activity determined by the composition of surface active sites. Monometallic gold catalyst was more effective in the hydrogen transfer in the case of substrates with competitive unsaturated functional groups.

KW - Alcohol amination

KW - Bimetallic catalyst

KW - Biomass

KW - Gold

KW - Hydrogen borrowing

KW - Myrtenol

KW - One-pot

KW - Palladium

KW - Redox treatment effect

KW - Terpenoids

UR - http://www.scopus.com/inward/record.url?scp=85073988457&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/425e18d2-7cd2-3366-b16b-630f45f898dd/

U2 - 10.1007/s10562-019-02958-6

DO - 10.1007/s10562-019-02958-6

M3 - Article

AN - SCOPUS:85073988457

VL - 149

SP - 3454

EP - 3464

JO - Catalysis Letters

JF - Catalysis Letters

SN - 1011-372X

IS - 12

ER -