MIYAMURA Hiroyuki


宮村 浩之みやむら ひろゆき
MIYAMURA Hiroyuki

MIYAMURA Hiroyuki
Title Assistant Professor
Affiliation Department of Chemistry (UG), Department of Chemistry (GR), Graduate School of Science
E-mail
Room Old Sci. No.1 Bldg. 2F 250
TEL +81-3-5841-4792 | 24792(ext.)


Research Field

Synthetic organic chemistry, Metal nano-cluster, Heterogeneous catalyst

Research Subject

(1) Grant-in-Aid for Scientific Research on Innovative Areas sponsored by The Ministry of Education, Culture, Sports, Science, and Technology, Japan (MEXT), “Organic Synthesis Based on Reaction Integration. Development of New Methods and Creation of New Substances” 04/2012 – 03/2014<br><br>(2) Grant-in-Aid for Young Scientists (B) sponsored by Japan Society for the Promotion of Science (JSPS), 04/2012 – 03/2014<br><br>(3) Grant-in-Aid for Scientific Research on Innovative Areas sponsored by The Ministry of Education, Culture, Sports, Science, and Technology, Japan (MEXT), “Organic Synthesis Based on Reaction Integration. Development of New Methods and Creation of New Substances” 04/2010 – 03/2012<br><br>(4) Grant-in-Aid for Young Scientists (B) sponsored by Japan Society for the Promotion of Science (JSPS), 04/2010 – 03/2012<br><br>(5) Grant-in-Aid for Research Activity start-up sponsored by Japan Society for the Promotion of Science (JSPS), 04/2009 – 03/2011 (refuse to accept during 04/2010 – 03/2011)

Current Research

Heterogeneous metal nanocluster (NC) catalysis has been of great interest in both academia and industry and has expanded rapidly because of these catalysts’ unique reactivity and selectivity, stability, recyclability and availability for reaction integration such as in continuous flow systems and tandem reactions. Also their activities and selectivities can be controlled by the formation of multimetallic NCs.<br><br>

In this context, we have aimed to develop versatile and reusable heterogeneous metal NCs in order to realize green organic transformations including tandem multistep processes especially under ambient conditions such as at room temperature and under atmospheric pressure. Our initial idea was simple; if metal NCs could be immobilized in hydrophobic environments of organic polymers, resulting catalysts might have high activity for general organic transformations.<br><br>

Firstly, we discovered that simple linear polystyrene could stabilize gold NCs that were prepared in an organic solvent by reduction. Secondly, we expanded this scientific knowledge to develop polymer incarcerated gold (PI-Au), in which gold NCs are locked up by polystyrene-based co-polymers with cross-linking moieties through physical envelopment of polymer backbones and the interactions between π electrons of benzene ring and nanocluster surface. We found that incorporating carbon black with high surface area (ketjen black) enabled increasing of metal loadings and catalytic activity of newly prepared catalysts (PI/CB-Au). Slight modification of the catalyst preparation method enabled formation of the immobilized bimetallic alloy NCs (PI-Au/Pt, PI-Au/Pd).<br><br>

Thus prepared PI-Au and multimetallic NC catalysts showed high activity for various oxidative transformations using molecular oxygen as oxidant, such as oxidation of alcohols to aldehydes and ketones, oxidation of hydroquinones to quinones, amines to imines, and hydroxylation of 1,3-dicarbonyl compounds under mild conditions. In addition, catalysts could be recovered and reused and could be applied to flow systems.<br><br>

Moreover, these catalysts could be successfully applied to tandem oxidation process (TOP), in which highly reactive, unstable and short-lived oxidized intermediates can be immediately consumed to give stable products in one-pot through following C-C or C-heteroatom bond formation reactions. We performed direct oxidative esterification reactions from two different alcohols, direct amides and imines synthesis from alcohols and amines, and tandem oxidation-Michael reaction.<br><br>

Recently we have developed a metalloenzyme-like cooperative catalytic system of PI/CB-Pt/Ir alloy NC and catechol derivatives for oxidation of amines to imines and synthesis of heterocyclic compounds. Furthermore, chiral Rh NC catalyzed asymmetric 1,4-addition reactions between enones and aryl boronic acids have been developed and it could be applied to TOP of aerobic oxidation and asymmetric C-C bond formation.

Keywords

Gold, Aerobic oxidation, Polymer immobilized catalyst, Heterogeneous catalyst, Environmentally benign organic synthesis, Metal nano-cluster

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