FY2015 Annual Report

Coordination Chemistry and Catalysis Unit
Assistant Professor Julia Khusnutdinova

Abstract

Coordination Chemistry and Catalysis group is interested in designing of new transition metal complexes for application as catalysts in reactions relevant to renewable energy production and for developing “green”, environmentally friendly methods in organic synthesis. The major directions in the Coordination Chemistry and Catalysis Unit are the following:

  1. Ligand design for mono- and polynuclear complexes for small molecule activation (CO2 hydrogenation; hydrogenation/dehydrogenation of alcohols and amines)
  2. Design of stimuli-reponsive polymers

1. Staff

  • Dr. Abhishek Dubey, Postdoctoral Scholar
  • Dr. Orestes Rivada Wheelaghan, JSPS Research Fellow
  • Dr. Georgy Filonenko, Postdoctoral Scholar
  • Dr. Pradnya Patil, Technician
  • Chika Azama, Research Unit Administrator

2. Collaborations

Nothing to report

3. Activities and Findings

Link to OIST news highlights: “One reaction, Two results, Zero waste”: http://www.oist.jp/news-center/news/2016/7/6/one-reaction-two-results-zero-waste

We reported a Ru-complex-catalyzed ester metathesis reaction where an unsymmetrical ester such as ethyl hexanoate can be transformed to a mixture of starting material, hexyl ethanoate, ethyl acetate, and hexyl hexanoate in equal proportions, as expected from a classical metathesis reaction with 0.2 mol % catalyst. A 20× excess of low boiling alcohol, such as ethanol, allows for the transfer of an acyl moiety to the sacrificial low boiling ethyl acetate product, while significantly increasing the functional group tolerance and substrate scope; yields of alcohols can reach 90%, which represents an attractive alternative to current high H2 pressure hydrogenation protocols for Ru-based ester reduction chemistry. Both reactions have not been reported previously in the field of Ru-catalyzed transformations of the ester functionality.

4. Publications

4.1 Journals

Khusnutdinova, J. R.; Milstein, D. "Metal-Ligand Cooperation" Angew. Chem. Int. Ed. 2015, 54,      
12236-12273, DOI: 10.1002/anie.201503873.

Dubey, A.; Khaskin, E. "Catalytic Ester Metathesis Reaction and Its Application to Transfer    
Hydrogenation of Esters" ACS Catal. 2016, 6, 3998–4002, DOI: 10.1021/acscatal.6b00827

4.2 Books and other one-time publications

Nothing to report

4.3 Oral and Poster Presentations

Khusnutdinova, J. R., Milstein, D., Utilizing water as the oxygen atom source: catalytic formation of lactams from amines, EuropaCat XII, Kazan, Russia, Sep 2 (2015).

Filonenko, G.; Khusnutdinova, J. R. Translating the stimuli response of the metal complexes with flexible macrocyclic ligands to the polymer materials. The 96th Chemical Society of Japan . meeting (日本化学会 第96春季年会), Kyotanabe campus, Doshisha University, Kyoto, Japan, March 27 (2016)

Khusnutdinova, J. R. Outline of Research at Coordination Chemistry and Catalysis Unit, Kyushu University-OIST Networking Event, OIST Campus, March 9, 2016

5. Intellectual Property Rights and Other Specific Achievements

Nothing to report

6. Meetings and Events

6.1 Seminar "Development of New Catalysts toward Utilization of 
     Renewable Resources"

  • Date: February 18, 2016
  • Venue: OIST Campus Lab3 (C700)
  • Speaker: Prof. Kyoko Nozaki, The University of Tokyo

6.2 Seminar “Towards the Silicon and Germanium Versions of Metathesis:
     Making M=C (M = Si, Ge) Bonds”

  • Date: December 11, 2015
  • Venue: OIST Campus Lab3 (C756)
  • Speakers: Prof. Vladimir Ya. LEE, University of Tsukuba

7. Other

Nothing to report.