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Details of Grant 

EPSRC Reference: EP/K00736X/1
Title: Gold-Catalysed Direct Allylic Etherification of Alcohols
Principal Investigator: Lee, Dr A
Other Investigators:
Macgregor, Professor SA
Researcher Co-Investigators:
Project Partners:
Department: Sch of Engineering and Physical Science
Organisation: Heriot-Watt University
Scheme: Standard Research
Starts: 11 March 2013 Ends: 14 April 2016 Value (£): 570,861
EPSRC Research Topic Classifications:
Asymmetric Chemistry Catalysis & Applied Catalysis
Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
Related Grants:
Panel History:
Panel DatePanel NameOutcome
25 Jul 2012 EPSRC Physical Sciences Chemistry - July 2012 Deferred
26 Sep 2012 EPSRC Physical Sciences Chemistry - September 2012 Announced
Summary on Grant Application Form
The synthesis of complex molecules of the type produced by the fine chemicals industry (e.g. pharmaceuticals and agrochemicals) often involves a sequence of challenging chemical transformations. As such it is vital that each of these steps is as efficient as possible. This means giving consideration to the ease of access to reactants, minimizing energy usage, and also minimizing any side products. Ideally, the reaction will selectively produce a single chemical in the form of the target material. Combining these desirable features will ultimately reduce the financial cost and environmental impact of the synthetic process to a minimum.

A general solution to these demands is the development of suitable catalysts that will allow reactions to occur under mild conditions with reduced (or easily handled) waste. In this proposal we seek to implement these ideas for a key general process in chemical synthesis: the synthesis of allylic ethers.

Our approach will be to develop a new gold-catalysed methodology for allylic ether formation that uses simple allylic alcohols as the starting point for synthesis. Allylic alcohols are cheap and readily available starting materials that do not require complicated prior synthesis. Our method uses gold to promote the reaction of the allylic alcohol with a second (different) alcohol molecule to form a new allylic ether. Under these circumstances a new C-O bond is formed and the only side product is environmentally benign water. We have preliminary results that demonstrate the feasibility of this process and that it occurs under mild conditions that are tolerant of air and moisture, suggesting our methods can be developed for wide use in synthesis.

The initial aim of our work is first to fully understand the way in which the direct allylic etherification reaction works and we will achieve this through a combination of experimental chemistry and computational modeling. The insight gained will then allow us to extend our catalytic process to produce more elaborate allylic ethers, with control of selectivity of the reaction in terms of the regio-, stereo-(E/Z) and ultimately enantioselectivity of the products. Ideally we will be able to form a single chemically useful form of a wide range of allylic ethers. A particularly challenging aspect is the development of enantioselective processes. Such reactions are not well established in gold-catalysis and we expect the insight we gain into such reactions will be relevant to a range of other reactions well beyond the specific allylic etherification that we will study here. We will also seek to extend our methods to other nucleophiles, by replacing the alcohols with different species that will permit new C-N and C-C bond forming reactions to be developed, that run under the favourable tolerant conditions of gold-catalysis.

The project will provide the basis for a new tool, for both synthetic organic chemistry and the fine chemicals industry, that is clean, energy economic and broad ranging in its applicability.

Key Findings
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Organisation Website: http://www.hw.ac.uk