Chemoselective Heterogeneous Iridium Catalyzed Hydrogenation of Cinnamalaniline | Sciact - CRIS-system of Boreskov Institute of Catalysis

Chemoselective Heterogeneous Iridium Catalyzed Hydrogenation of Cinnamalaniline Full article

Journal

Catalysis Science and Technology
ISSN: 2044-4753 , E-ISSN: 2044-4761

Output data

Year: 2021, Volume: 11, Number: 4, Pages: 1481-1496 Pages count : 16 DOI: 10.1039/D0CY01886D

Tags

Alumina; Aluminum oxide; Amines; Carbon carbon composites; Carbon nitride; Catalysis; Catalysts; Chlorine compounds; Computational geometry; Hydrogenation; Organic solvents; Porous materials; Potassium hydroxide; Pyrolysis; Silica; Toluene; Zirconia

Authors

Savela Risto ¹ , Shcherban Nataliya D. ² , Melander Marko M. ³ , Bezverkhyy Igor ⁴ , Simakova Irina L. ⁵ , Långvik Otto ¹ , Kholkina Ekaterina ⁶ , Schindler Tamara ¹ , Krauβ Annabelle ¹ , Honkala Karoliina ³ , Murzin Dmitry Yu. ⁶ , Leino Reko ¹

Affiliations

1	Johan Gadolin Process Chemistry Centre, Laboratory of Molecular Science and Technology, Organic Chemistry Research Group, Åbo Akademi University, FI-20500 Turku, Finland
2	L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 pr. Nauky, Kiev, 03028, Ukraine
3	Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland
4	Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université de Bourgogne-Franche Comté, 9 Av. A. Savary, BP 47870, 21078, Dijon Cedex, France
5	Boreskov Institute of Catalysis, pr. Ak. Lavrentieva 5, 630090, Novosibirsk, Russia
6	Johan Gadolin Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering, Åbo Akademi University, Turku, Finland

Funding (6)

1	Academy of Finland	307853
2	Academy of Finland	307623
3	Russian Foundation for Basic Research	18-53-45013
4	Federal Agency for Scientific Organizations	0303-2016-0012 (V.47.1.4.)
5	National Academy of Sciences of Ukraine	19/02-2020
6	Academy of Finland	295364

Selective hydrogenation of unsaturated imines over heterogeneous catalysts is an ecologically feasible and effective way to produce commercially valuable saturated imines and unsaturated amines under mild conditions, avoiding the utilization of toxic halides. The liquid-phase hydrogenation of a model imine, cinnamalaniline, over Ir, Ru, Pd and Au catalysts was studied in polar protic (methanol, 2-propanol), polar aprotic (methyl tert-butyl ether) and non-polar aprotic (toluene) solvents at 40–80 °C under atmospheric hydrogen pressure. Different metal oxides (Al2O3, ZrO2, SiO2) and carbon composites based on carbon nitrides synthesized by pyrolysis of ethylenediamine or melamine modified by KOH, HNO3, NH4Cl or TEOS (including template KIT-6), porous carbon (samples prepared by pyrolysis of sucrose, including template KIT-6) and mesoporous carbon Sibunit were applied to study the effect of the support. Among the tested metals, iridium exhibited the most promising catalytic performance in terms of hydrogenation activity and chemoselectivity towards unsaturated amine. The use of Ir on carbon nitrides (C3N4–NH4Cl, CxNy-KIT-6) and amphoteric metal oxides (ZrO2, Al2O3) in nonpolar aprotic toluene solvent provided the best selectivity towards unsaturated amine by minimizing oligomerization. Computational studies indicate that the selective hydrogenation of the C[double bond, length as m-dash]N group on Ir results from a favorable cinnamalaniline adsorption geometry at high surface coverage. Comparable heterogeneously catalyzed highly chemoselective hydrogenation of unsaturated imine into unsaturated amine under atmospheric hydrogen pressure and low temperatures has not been reported previously.

Savela R. , Shcherban N.D. , Melander M.M. , Bezverkhyy I. , Simakova I.L. , Långvik O. , Kholkina E. , Schindler T. , Krauβ A. , Honkala K. , Murzin D.Y. , Leino R.
Chemoselective Heterogeneous Iridium Catalyzed Hydrogenation of Cinnamalaniline

Catalysis Science and Technology. 2021. V.11. N4. P.1481-1496. DOI: 10.1039/D0CY01886D WOS Scopus РИНЦ AN OpenAlex

Full text from publisher

Submitted:	Sep 25, 2020
Accepted:	Dec 1, 2020
Published online:	Dec 9, 2020
Published print:	Feb 21, 2021

Web of science:	WOS:000624503000023
Scopus:	2-s2.0-85102025834
Elibrary:	46805013
Chemical Abstracts:	2020:2536145
OpenAlex:	W3111077280

DB	Citing
Scopus	2
Web of science	3
Elibrary	2
OpenAlex	3