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AFFORDABLE SOLUTIONS FOR ASYMMETRIC REDUCTIONS OF INDUSTRIALLY RELEVANT SUBSTRATES

Project
A number of methods exist for the production of enantiopure pharma intermediates. Among them, classical resolution by crystallization is the least efficient and most used one, while asymmetric catalysis, arguably the most efficient, is much less used. This paradox is due to a number of factors, such as: 1. High cost of the catalyst. 2. Lack of scope. 3. Time-to-market pressure. In this project we will investigate solutions to problems 1 and 2. We will develop new chiral catalysts for asymmetric double bond reduction that contain first-row base metals (e.g. Fe, Cu, Co, Ni). These metals are remarkably cheaper than their second and third-row noble metal counterparts (e.g. Ru, Rh, Ir, Pd, Pt). The chiral ligands should form strong bonds with these base metals in order to prevent the disabling metathesis of the complexes. In these complexes, we will also explore the use of non-innocent ligands which can participate in the transfer of electrons. The chiral ligands should be ideally produced in a few steps at low cost. According to a combinatorial approach, we will use libraries of ligands and of metal sources, so that the best hit can be rapidly identified. The second problem we want to address is the enantioselective reduction of pyridines, that so far have defied attempts at their asymmetric reduction to 2- or 3-substituted piperidines, which are important pharma intermediates. Disturbing the aromaticity of the pyridines via quaternization, or via binding to a metal surface or via eta6-binding to another metal complex will activate them for asymmetric reduction via catalytic hydrogenation or transfer hydrogenation. Our aim is to train two PhD researchers aware of the importance of sustainability issues (use of readily available metals, study of life cycle analysis assessment, carbon footprint evaluation) as well as expert in the use and combination of different catalytic methodologies as important tools for the responsible production of commodity and fine chemicals.
  • Academic Signature
  • Overview
  • Research Areas
  • Publications

Academic Signature

Il servizio di classificazione ACADEMIC SIGNATURE è IN BETA TESTING e i risultati potrebbero non essere corretti

Academic Signature (4)

Crystallization
Chemical Phenomena
Combinatorial Chemistry Techniques
Chemistry Techniques, Synthetic
Piperidines
Heterocyclic Compounds, 1-Ring
Hydrogenation
Organic Chemistry Phenomena

Overview

Contributors

PIGNATARO LUCA LUIGI   Participant  

Departments involved

Dipartimento di Chimica   Principale  

Type

7PQ_MC - 7 Programma Quadro_Marie Curie ITN_IEF_IOF_IIF_IAPP

Funder

EUROPEAN COMMISSION
External Organization Funding Organization

Date/time interval

October 1, 2012 - September 30, 2016

Project duration

48 months

Research Areas

Concepts (3)


PE5_13 - Homogeneous catalysis - (2013)

PE5_17 - Organic chemistry - (2013)

PE5_19 - Combinatorial chemistry - (2013)

Keywords (5)

  • ascending
  • descending
CHEMICAL REACTIONS
COMBINATORIAL CHEMISTRY
HOMOGENEOUS CATALYSIS
METHOD DEVELOPMENT IN CHEMISTRY
ORGANIC CHEMISTRY
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Publications

Outputs (6)

Synthesis of [bis(hexamethylene)cyclopentadienone]iron tricarbonyl and its application to catalytic reductions of C=O bonds 
CHEMCATCHEM
WILEY
2017
Academic Article
Partially Open Access
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A Mixed Ligand Approach for the Asymmetric Hydrogenation of 2-Substituted Pyridinium Salts 
ADVANCED SYNTHESIS & CATALYSIS
WILEY
2016
Academic Article
Partially Open Access
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Asymmetric Transfer Hydrogenation of Ketones with Modified Grubbs Metathesis Catalysts : on the Way to a Tandem Process 
ADVANCED SYNTHESIS & CATALYSIS
WILEY
2016
Academic Article
Partially Open Access
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Asymmetric hydrogenation of 3-substituted pyridinium salts 
CHEMISTRY-A EUROPEAN JOURNAL
WILEY
2016
Academic Article
Partially Open Access
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Riding the Wave of Monodentate Ligand Revival : from the A/B Concept to Noncovalent Interactions 
THE CHEMICAL RECORD
WILEY
2016
Academic Article
Partially Open Access
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Synthesis of (R)-BINOL-derived (cyclopentadienone)iron complexes and their application in the catalytic asymmetric hydrogenation of ketones 
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
WILEY
2015
Academic Article
Reserved Access
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