Organic transformations: selective processes and asymmetric catalysis

Objetivo

A.GENERAL BACKGROUND

A1: Why a COST action for this topic

Organic reactions and processes play an important role in the chemical industry. The development of new, selective, organic transformations has led to great improvements in the production of chemical substances over the years. The increased need for tailored molecules with specific functions or properties requires the continuous devleopment of new synthetic methods. In the pharmaceutical and fine chemical industries there is a demand for selective synthesis of bioactive compounds, pharmaceuticals, and agricultural agents. Often these compounds are required in enantiomerically pure form, which has been achieved via asymmetric synthesis.

For large-scale chemical production there is a demand for selective organic transformations which make efficient economic use of feedstock and energy. It is also essential that these organic processes are environmentally friendly and produce the minimum amount of waste.

One field of particular importance within this action is asymmetric catalysis, including both enzyme and transition metal catalysis. At present this field is dominated by research groups in the USA and Japan. It is therefore important to strengthen the European competence in this area. There is currently intense activity focused on asymmetric catalysis in a number of European laboratories and a coordination of these activities via a COST Action is crucial for the future development of the field.

A2: Status of Research in the Field

The field of research has undergone intensive development during the last decade. Major achievements have been obtained with the use of transition metal catalysis which is currently a strongly expanding field. The use of enzyme catalysis for selective organic transformations is also emerging as an important sub-field. the following list provides representative topics within the research field of the proposed Action:

Metal-catalyzed enantioselective reactions

Ligand design in asymmetric catalysis

Enzymes in asymmetric catalysis

New metal-catalyzed oxidation reactions

Stereo- and regio-control in organic transformations

Development of environmentally friendly oxidation reactions which employ molecular oxygen or hydrogen peroxide

Heterogeneous catalysis in the synthesis of fine chemicals

Homogeneous catalysis for mild and selective organic transformations

Chirality transfer in organic reactions

Catalytic processes for production of organic molecules on a large scale

Total synthesis of biologically active compounds of interest

Radical reactions in selective organic transformations

The use of chiral auxiliaries in asymmetric synthesis

Studies on the mechanism of transition metal-catalyzed organic reactions

Mechanistic aspects on catalytic enantioselective reactions

The use of catalytic antibodies in stereoselective organic transformations

Development of new catalysts and reagents for selective organic transformations

A3: Relationship with other European Programmes

There is no particular specific European programme devoted to organic chemistry exclusively, except that COST Action D2 on "Selective Synthesis" is complementary to, and has initiated, this new Action. In fact the proposed new Action is a follow-up to the previous D2 Action but with more focus on asymmetric catalysis and organic process of interest to the chemical industry. Also COST Action D7 on "Molecular Recognition Chemistry", and the proposed Actions on Supramolecular Chemistry" and "Bioorganic Chemistry for Pharmaceutical and Medicinal Applications" are complementary to the proposed new Action. Interactions with these related Actions will take place via the COST Chemistry Technical Committee and planned joint workshops.

B.OBJECTIVES OF THE ACTION AND SCIENTIFIC CONTENT

B1: Main Objective

The main objective of the proposed COST Action is to develop new, efficient, and selective organic transformations which can be used to obtain desired molecules with special functions and properties.

B2: Sub-Tropics

1.Catalytic asymmetric synthesis based on the use of transition metals

The objective is to study and develop new, catalytic, enantioselective organic reactions. These reactions may be based on chiral homogeneous catalysts such as transition metal complexes. They may also employ a chiral heterogeneous transition metal catalyst. The latter catalysts may be immobilized homogeneous catalysts or a metal surface with a chiral modifier.

Within this sub-topic, projects on ligand design for asymmetric catalysis will be included.

It is important to understand the mechanism of these reactions (at the molecular level) and the origin of enantioselectivity. Therefore, experimental studies will be combined with mechanistic studies.

2.Selective processes based on the use of enzymes or catalytic antibodies

The objective is to develop new selective processes that are catalyzed by enzymes or antibodies. The enzymes may be bioenzymes or artificial enzymes.

One major application of enzyme and antibody catalysis will be asymmetric synthesis. In addition to direct application for enantioselective organic transformations, projects studying the chiral discrimination of these catalysts will be included in this programme. Projects concerned with artificial enzymes and antibodies may lead to interesting "unnatural" selectivities (e.g. stereo- and regioselectivities) in organic transformations.

3.Studies and development of organic transformations via reactive intermediates (radicals, carbenes, carbocations etc.)

The objective is to develop new selective reactions based on the use of reactive intermediates which can be generated by different means.

Projects on stereoselective reactions via radicals or carbenes are included in this project.

4.Transition metal mediated and catalyzed organic synthesis

The objective is to develop new and selective organic reactions based on the use of transition metal catalysis.

Promising contributions are expected from the burgeoning fields of metallorganic chemistry including the particularly attractive field of organic transition metal complexes which has already provided a cornucopia of extremely useful catalytic processes. Metal complexes of, for instance, palladium, platinum, rhodium, ruthenium, osmium, copper, and even silver and gold, are offering many possibilities for the directed formation of carbon-carbon bonds, but also for reductions and oxidations, as well as methathesis and olefination processes in general.

The programme also includes reactions which employ environmentally friendly oxidants such as molecular oxygen, hydrogen peroxide and other peroxides. Of special interest will be the development of mild transition metal catalyzed aerobic oxidations.

5.New strategies for the synthesis of complex molecules

The objective is to synthesize, with atom economy and in an elegant manner, complex molecules via selective and efficient methods.

In many instances there is the necessity to synthesize a great number of well defined and in many cases extremely complex molecules which require substantial innovations in synthetic methodology and for much wider development of existing techniques. To attain these goals, one will have to focus particularly on the development of those methods that offer the means to form carbon-carbon bonds under mild conditions and with high efficiency as well as those transformations that guarantee high flexibility in the predictable manipulation of heteroatoms and functional groups.

Projects on the total synthesis of important biologically active compounds are included in this programme. For efficient strategies, atom-economy is of importance. Examples of atom economical reactions are pericyclic reactions and concerted processes.

C.SCIENTIFIC PROGRAMME

The scientific programme will depend on the projects submitted by individual research teams. The successful projects will be selected according to the objectives outlined above. At this stage there is no specific scientific programme suggested for this action in order to place no limitations on the invited proposals. The selection will strictly occur according to the outlined objectives.

D.ORGANIZATION AND TIMETABLE

D1:Organization

Research projects fitting in the sub-topics described in section C will be submitted by scientists to the Management Committee members. This Committee will establish contacts between scientists. The organizational structure can be illustrated as follows:

The Management Committee has responsibilities for:

1.Drawing up the inventory during the first year, organization of workshops and start of the activity; existing contacts will be used which should greatly facilitate this task.

2.The coordination of the joint activities with other COSTS Actions; joint meetings are likely to result from this activity.

3.Exploration of wider participation and exchange of information with EC-specific programmes, ESF, etc.

4.The planning of the intermediate report, the final report and the concluding symposium.

Progress in each of the projects will also be reported by the respective participants in their own countries within the framework of existing programmes.

D2:Reports

The progress of the programme will be monitored by brief annual reports from each of the participating scientists which will describe the results of research obtained through concertation. A milestone report will be prepared by the Management Committee after 3 years of joint activities. The report will be presented to the COST Technical Committee for Chemistry for their review.

A final report will be published to inform non-participating scientists and research workers interested in the results about the scientific achievements of the Action. It is expected that some reviews by participants which describe the progress made and state of the field will be published in International Journals. To conclude the COST Action, a symposium will be held after 5 years which will be accessible to other scientists.

D3:Timetable

The Action will last five years and comprise the following four stages:

Stage 1:After the first meeting of the Management Committee, a detailed inventory of ongoing research and existing plans of the participating groups to begin joint projects will be made. This will result in a discussion document which will allow further planning to occur.

Stage 2:It will be evident which projects are closely related and would benefit from joint activities. Researchers (and co-workers) will set up (and continue) joint collaborative projects and exchange their recent research results. It may be appropriate to explore wider collaboration with other European countries during this stage.

Stage 3:An intermediate progress report will be prepared after 3 years for review by the COST Technical Committee for Chemistry and by the COST Senior Officials Committee.

Stage 4:This final phase will begin after 4 years and will involve the evaluation of the results obtained. It may include the organization of a symposium for all the participants and co-workers.

E.ECONOMIC DIMENSIONS

The economic dimension of the Action (initial estimate of total costs = personnel + operational + running + commission costs) is: ECU 41 million.

The human effort in the area of "Organic Transformations: Selective processes and Asymmetric Catalysis", as described in this document, amounts to 850 man-years, being equivalent to ECU 36 million approximately.

E1:Personnel costs

Estimates of personnel costs (research + administration) will depend on the rates applicable for various EU countries (estimate ECU 41 million + ECU 9 million = ECU 50 million).

Estimates of personnel costs (research + administration) are as follows:

Sub-topic 1:in about 17 countries a total of 260 man-years, totalling ECU 11 million
Sub-topic 2:in about 11 countries a total of 130 man-years, totalling ECU 5,5 million
Sub-topic 3:in about 10 countries a total of 90 man-years, totalling ECU 3,8 million
Sub-topic 4:in about 18 countries a total of 210 man-years, totalling ECU 8,9 million
Sub-topic 5:in about 18 countries a total of 160 man-years, totalling ECU 6,8 million

E2:Operational and running costs

The estimate of the total operational and running costs including costs of instruments and materials is ECU 5 million.

E3:Coordination costs

The costs of coordination to be covered by the COST budget are estimated to be 60 kECU per year, i.e. a total of 300 kECU for the five year duration of the project.

Programa(s)

IC-COST - European cooperation in the field of scientific and technical research (COST), 1971-

Tema(s)

13 - Chemistry

Convocatoria de propuestas

Data not available

Régimen de financiación

Data not available

Coordinador

N/A

Aportación de la UE

Sin datos

Dirección

Suiza

Coste total