Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:

 

A novel “Kabuto-like” nickel catalyst forms bioactive frameworks from low-cost phenol derivatives

28.05.2014

Researchers at ITbM developed a new nickel catalyst with a “Kabuto-like” structure that catalyzed the cross-coupling reaction between carbonyl compounds and readily available phenol derivatives, to form α-arylketones, which are found in many biologically active compounds.

Researchers at ITbM, Nagoya University developed a new nickel catalyst with a “Kabuto-like” structure that was found to catalyze the cross-coupling reaction between carbonyl compounds and readily available phenol derivatives, to form α-arylketones, which are found in many biologically active compounds (Kabuto = a helmet worn by Japanese samurai).


Framework for pharmaceuticals and organic materials

Copyright : ITbM, Nagoya University


Structural optimization of nickel catalyst

Copyright : ITbM, Nagoya University


Bio-active compounds containing a carbonyl aryl structure

Nagoya, Japan – Professors Kenichiro Itami and Junichiro Yamaguchi of the Institute of Transformative Bio-Molecules (WPI-ITbM) and graduate students Ryosuke Takise and Kei Muto of Nagoya University have succeeded in developing a novel nickel catalyst to catalyze the cross-coupling reaction between carbonyl compounds and phenol derivatives.

Phenol derivatives are known to be readily available starting materials, and this reaction has enabled the facile generation of α-arylketone compounds (aryl = aromatic ring; ketone = a carbonyl (C=O functionality with a carbon oxygen double bond) bonded to two other carbon atoms), which constitute the framework of many pharmaceuticals and organic materials.

The study published online on May 20, 2014 in Angewandte Chemie International Edition, is expected to become an important tool in synthesizing biologically active molecules and a range of versatile organic materials containing the α-arylketone framework.

Cross-coupling reactions catalyzed by transition metals enables direct formation of carbon-carbon bonds, which is widely utilized in the formation of a vast number of organic frameworks. This strategy that won the 2010 Nobel Prize in Chemistry extends to α-arylation reactions, which allows incorporation of aromatic rings into carbonyl compounds through carbon-carbon bond formation, mainly using palladium as a catalyst. Many organic molecules such as amino acids contain carbonyl groups.

Thus, α-arylation, which links carbonyl compounds to aromatic rings present in an array of organic molecules, has been used as one of the main reactions to create the organic backbone of many pharmaceuticals and organic materials. Professors Itami and Yamaguchi along with co-workers have been working to develop a new economical catalyst to conduct α-arylation reactions using readily available phenol derivatives as starting materials. This reaction system is envisaged to lead to the facile production of α-arylketones on an industrial scale.

Conventional methods for α-arylation have used palladium as a metal catalyst. “Since 2009, we have been looking at the potential of nickel as a cross-coupling catalyst, which is a more economical catalyst relative to palladium”, says Professor Yamaguchi, one of the leaders of this research, “through our endeavors to develop improved conditions, we have found that phenol derivatives can act as readily available aryl coupling partners”, he describes. Aryl substrates have mainly utilized aryl halides, which are halogenated compounds resulting in toxic wastes. Phenol derivatives on the other hand are usually less toxic and are more readily available compared to aryl halides.

Itami and his group have been working on the development of new generation cross-coupling methods using nickel as a catalyst. They have already reported various cross-coupling reactions including those between aromatic compounds and phenol derivatives, C-H coupling reactions using esters along with reactions linking aromatic rings and alkenes. These pioneering studies have been accomplished by enhancing the reactivity of nickel through tuning of various ligands. One of the effective ligands discovered in 2011 is the dcype (1,2-bisdicyclohexylphosphinoethane) ligand, which is used with nickel to activate phenol derivatives. However, the nickel(dcype) catalyst was insufficient to initiate the cross-coupling between carbonyl compounds and phenol derivatives.

“We have screened various ligands and found that dcypt (1,2-bisdicyclohexylphosphinothiophene), which bears a thiophene (a 5-membered heterocycle containing sulfur) unit, acts as an effective air-stable ligand to improve the reactivity of nickel and bring about this reaction in high yield. Moreover, we were able to use a weak base to carry out this reaction, which improves the substrate scope of this reaction”, explains graduate students Takise and Muto who carried out the experiments.

Development of this new nickel catalyst has enabled the creation of a variety of α-arylketone compounds, including an estrone derivative and an amino acid tyrosine derivative, both bearing the phenol moiety. Professor Itami elaborates, “Many natural products and bioactive compounds contain the α-arylketone framework. Our relatively low-cost nickel-dcypt catalyst has exhibited high activity to couple readily available phenol derivatives in high yield. This system has the potential to be applicable in the synthesis of molecules that can control biological systems of plants and animals, which is one of the main research themes running in our new institute (ITbM).”

This article “Nickel-Catalyzed α-Arylation of Ketones with Phenol Derivatives” by Ryosuke Takise, Kei Muto, Junichiro Yamaguchi and Kenichiro Itami is published online on May 20, 2014 in Angewandte Chemie International Edition.
DOI: 10.1002/anie.201403823

About WPI-ITbM (http://www.itbm.nagoya-u.ac.jp/)
The World Premier International Research Center Initiative (WPI) for the Institute of Transformative Bio-Molecules (ITbM) at Nagoya University in Japan is committed to advance the integration of synthetic chemistry, plant/animal biology and theoretical science, all of which are traditionally strong fields in the university. As part of the Japanese science ministry’s MEXT program, the ITbM aims to develop transformative bio-molecules, innovative functional molecules capable of bringing about fundamental change to biological science and technology. Research at the ITbM is carried out in a “Mix-Lab” style, where international young researchers from multidisciplinary fields work together side-by-side in the same lab. Through these endeavors, the ITbM will create “transformative bio-molecules” that will dramatically change the way of research in chemistry, biology and other related fields to solve urgent problems, such as environmental issues, food production and medical technology that have a significant impact on the society.

Author Contact
Professor Kenichiro Itami
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University
Furo-Cho, Chikusa-ku, Nagoya 464-8601, Japan
TEL/FAX: +81-52-788-6098
E-mail: itami@chem.nagoya-u.ac.jp
URL for Group Homepage: http://synth.chem.nagoya-u.ac.jp/
URL for ITbM Homepage: http://www.itbm.nagoya-u.ac.jp/

Public Relations Contact
Dr. Ayako Miyazaki
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University
Furo-Cho, Chikusa-ku, Nagoya 464-8601, Japan
TEL: +81-52-789-4999 FAX: +81-52-789-3240
E-mail: press@itbm.nagoya-u.ac.jp

Nagoya University Public Relations Office
TEL: +81-52-789-2016 FAX: +81-52-788-6272
E-mail: kouho@adm.nagoya-u.ac.jp

Ayako Miyazaki | Research SEA News
Further information:
http://www.researchsea.com

Further reports about: Nagoya amino aromatic bioactive catalyst compounds ligands materials reaction

More articles from Life Sciences:

nachricht IU-led study reveals new insights into light color sensing and transfer of genetic traits
06.05.2016 | Indiana University

nachricht Thievish hoverfly steals prey from carnivorous sundews
06.05.2016 | Staatliche Naturwissenschaftliche Sammlungen Bayerns

All articles from Life Sciences >>>

The most recent press releases about innovation >>>

Die letzten 5 Focus-News des innovations-reports im Überblick:

Im Focus: Nuclear Pores Captured on Film

Using an ultra fast-scanning atomic force microscope, a team of researchers from the University of Basel has filmed “living” nuclear pore complexes at work for the first time. Nuclear pores are molecular machines that control the traffic entering or exiting the cell nucleus. In their article published in Nature Nanotechnology, the researchers explain how the passage of unwanted molecules is prevented by rapidly moving molecular “tentacles” inside the pore.

Using high-speed AFM, Roderick Lim, Argovia Professor at the Biozentrum and the Swiss Nanoscience Institute of the University of Basel, has not only directly...

Im Focus: 2+1 is Not Always 3 - In the microworld unity is not always strength

If a person pushes a broken-down car alone, there is a certain effect. If another person helps, the result is the sum of their efforts. If two micro-particles are pushing another microparticle, however, the resulting effect may not necessarily be the sum their efforts. A recent study published in Nature Communications, measured this odd effect that scientists call “many body.”

In the microscopic world, where the modern miniaturized machines at the new frontiers of technology operate, as long as we are in the presence of two...

Im Focus: Tiny microbots that can clean up water

Researchers from the Max Planck Institute Stuttgart have developed self-propelled tiny ‘microbots’ that can remove lead or organic pollution from contaminated water.

Working with colleagues in Barcelona and Singapore, Samuel Sánchez’s group used graphene oxide to make their microscale motors, which are able to adsorb lead...

Im Focus: ORNL researchers discover new state of water molecule

Neutron scattering and computational modeling have revealed unique and unexpected behavior of water molecules under extreme confinement that is unmatched by any known gas, liquid or solid states.

In a paper published in Physical Review Letters, researchers at the Department of Energy's Oak Ridge National Laboratory describe a new tunneling state of...

Im Focus: Bionic Lightweight Design researchers of the Alfred Wegener Institute at Hannover Messe 2016

Honeycomb structures as the basic building block for industrial applications presented using holo pyramid

Researchers of the Alfred Wegener Institute (AWI) will introduce their latest developments in the field of bionic lightweight design at Hannover Messe from 25...

All Focus news of the innovation-report >>>

Anzeige

Anzeige

Event News

The “AC21 International Forum 2016” is About to Begin

27.04.2016 | Event News

Soft switching combines efficiency and improved electro-magnetic compatibility

15.04.2016 | Event News

Grid-Supportive Buildings Give Boost to Renewable Energy Integration

12.04.2016 | Event News

 
Latest News

Expanding tropics pushing high altitude clouds towards poles, NASA study finds

06.05.2016 | Earth Sciences

IU-led study reveals new insights into light color sensing and transfer of genetic traits

06.05.2016 | Life Sciences

Thievish hoverfly steals prey from carnivorous sundews

06.05.2016 | Life Sciences

VideoLinks
B2B-VideoLinks
More VideoLinks >>>