Development of Heterogeneous Metal Catalysts for Selective Oxidation and C-H Functionalization using Molecular Oxygen

2014 Fiscal Year Final Research Report

• Project/Area Number: 25810108
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Green/Environmental chemistry
• Research Institution: Tokyo Metropolitan University (2014); Kyushu University (2013)
• Principal Investigator: ISHIDA Tamao 首都大学東京, 都市環境科学研究科, 特任教授 (90444942)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Keywords: 金属ナノ粒子 / C-H官能基化 / カップリング / 金属酸化物

Outline of Final Research Achievements

Zirconia supported palladium hydroxide showed the highest catalytic activity for intramolecular C-H/C-H coupling of diphenylamine to carbazole.
In contrast, cobalt oxide and zirconia supported gold nanoparticle catalysts exhibited the highest catalytic activity for intermolecular C-H/C-H coupling of dimethyl phthalate to give the corresponding biaryl dimers using molecular oxygen as a sole oxidant. Gold catalysts also showed excellent regioselectivity to the symmetrical biaryl derivatives without the addition of ligands and co-catalysts. Substrate scope and kinetic studies revealed that the oxidative coupling proceeded via a nucleophilic aromatic substitution reaction. Gold nanoparticles act not only as catalytic active species but also as bulky ligands to control the regioselectivity of products.
For ammoximation of cycloalkanones using ammonia and molecular oxygen, titania supported gold catalysts showed the highest catalytic activity to give the corresponding cycloalkanoneoximes.

Free Research Field

固体触媒化学