Delivering Hydroacylation as a General Reaction for Synthesis: A Combined Organic and Organometallic Approach
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
The hydroacylation of alkenes and alkynes is a fundamentally simple process involving the addition of an aldehyde across and alkene or an alkyne to generate a ketone-containing product. Although a number of metal catalysts are known to promote the reaction the majority of these systems are inefficient, require harsh reaction conditions and have limited substrate scope. The aim of this proposal is to develop new catalysts systems that will allow the process to deliver products in high yields, using stable, easy to handle complexes that operate under mild conditions, and that function for a wide range of organic substrates. To arrive at this point we propose a collaborative program of research involving both organic and inorganic chemists. We will design new classes of ligands and catalysts that allow stabilisation of the key reactive metal-centre while still allowing the reaction to proceed. Preliminary results from our laboratories have shown that such an approach is valid. Along with catalyst design we will study the mechanism of the process using a variety of characterisation methods, and will build up a detailed understanding of the individual steps of the reaction. This mechanistic information will then be fed into the catalysts design loop to deliver yet more effective catalysts. Applications of the proposed chemistry includes the efficient synthesis of ketone and enone systems, ring-closing reactions to generate cyclic ketones, and the potential application of the chemistry to the synthesis of new polymeric materials.
Publications
Parsons S
(2011)
O -Substituted Alkyl Aldehydes for Rhodium-Catalyzed Intermolecular Alkyne Hydroacylation: The Utility of Methylthiomethyl Ethers
in Organic Letters
Arambasic M
(2013)
Activating group recycling in action: a rhodium-catalyzed carbothiolation route to substituted isoquinolines.
in Organic letters
Pawley R
(2012)
Intermolecular Alkyne Hydroacylation. Mechanistic Insight from the Isolation of the Vinyl Intermediate That Precedes Reductive Elimination
in Organometallics
Description | Efficient new catalysts for intermolecular hydroacylation |
Exploitation Route | These catalysts will be use by others |
Sectors | Agriculture, Food and Drink,Chemicals,Pharmaceuticals and Medical Biotechnology |