N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
Synthetic chemistry is used for the preparation of structurally complex materials on a molecular scale. Complexity in molecules is often associated with chirality - the fundamental property of a structure that renders it non-superimposable on its mirror image. For example, your right hand is chiral because it cannot be superimposed upon its mirror image (your left hand); the right hand is called the enantiomer of the left hand. Chirality also has important consequences, as it means that a right-handed glove cannot be worn on the left hand. This concept of chirality extends to the molecular level, where molecules can exist in two forms that differ only in that the arrangement of their atoms make them mirror images; indeed the majority of biochemical processes involve the interaction of chiral molecules that can exist in non-superimposable mirror image (enantiomeric) forms. This proposal investigates the application of a simple class of chiral organic molecule, known as N-heterocyclic carbenes, for their ability to catalyse selectively the formation of a single enantiomer of a given substance. A modular approach to the design and preparation of these reactive molecules that contain the necessary function and structure to promote catalysis will be used to succeed in this area. The effect of changing the structure of the N-heterocyclic carbene upon its reactivity will also be probed, and the application of these results to asymmetric synthesis and new chemical transformations investigated.
Publications
Richmond E
(2015)
An asymmetric pericyclic cascade approach to 3-alkyl-3-aryloxindoles: generality, applications and mechanistic investigations.
in Organic & biomolecular chemistry
Maji B
(2011)
Nucleophilicities and Lewis basicities of isothiourea derivatives.
in The Journal of organic chemistry
Ling KB
(2011)
a-Aroyloxyaldehydes: scope and limitations as alternatives to a-haloaldehydes for NHC-catalysed redox transformations.
in Chemical communications (Cambridge, England)
Joannesse C
(2009)
Isothiourea-catalyzed enantioselective carboxy group transfer.
in Angewandte Chemie (International ed. in English)
Joannesse C
(2012)
Isothiourea-mediated asymmetric O- to C-carboxyl transfer of oxazolyl carbonates: structure-selectivity profiles and mechanistic studies.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Joannesse C
(2008)
Amidine catalysed O- to C-carboxyl transfer of heterocyclic carbonate derivatives.
in Organic & biomolecular chemistry
Concellón C
(2009)
N-Heterocyclic Carbene-Mediated Enantioselective Addition of Phenols to Unsymmetrical Alkylarylketenes
in Advanced Synthesis & Catalysis
Belmessieri D
(2011)
Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]benzothiazole-based isothioureas as enantioselective acylation catalysts.
in Organic & biomolecular chemistry
Description | This research grant allowed to probe, develop, and understand the reactivity of two classes of molecules, called N-heterocyclic carbenes and isothioureas, in making molecules of pharmaceutical interest. |
Exploitation Route | The reactivity showed by these molecules provided a platform for the development of new reaction methodologies that have been exploited in industrial collaborations and in research groups around the world. |
Sectors | Chemicals,Pharmaceuticals and Medical Biotechnology |
Description | Some of the catalysts developed and utilised in this research have been utilised by a commercial agrochemical company in order to make compounds of significant biological interest. |
Sector | Agriculture, Food and Drink,Chemicals,Pharmaceuticals and Medical Biotechnology |
Impact Types | Societal |
Description | Research partnership - Herbert Mayr (LMU Munich) |
Organisation | Ludwig Maximilian University of Munich (LMU Munich) |
Department | University Clinic of Munich |
Country | Germany |
Sector | Academic/University |
PI Contribution | Research partnership that led to exchange of students and led to numerous joint publications |
Collaborator Contribution | Exchange of methodology and research placement for students to benefit knowledge exchange |
Impact | A number of joint publications serve as joint outputs from this collaboration |
Start Year | 2010 |