Enantioselective New Metal-Catalysed Carbocyclisation Reactions
Lead Research Organisation:
University of Liverpool
Department Name: Chemistry
Abstract
The ability to systematically vary the three-dimensional structure of pharmacophores present in biologically interesting molecules provides a critical and unsolved challenge for synthetic chemistry. This may be attributed to the fact that even relatively simple deviations in functionality present unforeseen problems that significantly limit the productive translation of a particular methodology into a related system of potential interest. Transition metal-catalysed multi-component carbocyclisation reactions represent an important class of reactions, due in part to their ability to construct polycyclic systems that are generally not accessible via classical pericyclic reactions. The importance of this class of transformations is evident from the exponential growth in this field over the last decade, albeit underrepresented within the United Kingdom and largely dominated by large research groups in other countries, i.e. United States, France, Japan, Korea, etc. Although many of these developments highlight the versatility of transition metal-catalysed reactions, through catalyst tuning via steric and electronic modifications to the ligand, there is still a need to garner a fundamental understanding of the guiding principles that control a specific transformation. Notwithstanding these limitations the reactions are generally atom economical with broad substrate scope, and proceed under relatively mild conditions, which reduces waste byproducts, allows traditionally unreactive substrates to be utilised and minimises energy costs. Furthermore, the complex nature of these reactions provides an outstanding area to educate highly skilled individuals and disseminate the work in high impact journals, which will significantly advance the United Kingdom's standing in this particular research area.
Organisations
Publications
Crandell DW
(2015)
The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects.
in Chemical science
Evans PA
(2015)
Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.
in Angewandte Chemie (International ed. in English)
Evans PA
(2013)
A concise total synthesis of pyrovellerolactone using a rhodium-catalyzed [(3 + 2) + 2] carbocyclization reaction.
in Organic letters
Inglesby PA
(2014)
The isolation and characterization of a rhodacycle intermediate implicated in metal-catalyzed reactions of alkylidenecyclopropanes.
in Angewandte Chemie (International ed. in English)
Mazumder S
(2012)
Stereoselective rhodium-catalyzed [3 + 2 + 1] carbocyclization of alkenylidenecyclopropanes with carbon monoxide: theoretical evidence for a trimethylenemethane metallacycle intermediate.
in Journal of the American Chemical Society
Description | Bonds between carbon atoms are the skeletons of organic molecules used in fuel, medicines and pesticides. They are buried and normally quite inert, thus typically difficult to manipulate. Using metal catalysts, our studies have taught us how we cleave and form those bonds in a controlled manner. |
Exploitation Route | The findings resulting from this study can be useful for the efficient manufacture of molecules in all branches of the fine chemical industry. |
Sectors | Aerospace, Defence and Marine,Agriculture, Food and Drink,Chemicals,Pharmaceuticals and Medical Biotechnology |