Details of Grant 

EPSRC Reference:	EP/L012855/1
Title:	Understanding the Platinum-Catalysed Reaction of Allenes with Nucleophiles: Towards New Reactivities and Novel Structures
Principal Investigator:	Munoz-Herranz, Dr M
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	University of East Anglia
Scheme:	First Grant - Revised 2009
Starts:	24 March 2014	Ends:	23 September 2015	Value (£):	99,629
EPSRC Research Topic Classifications:	Catalysis & Applied Catalysis Chemical Synthetic Methodology Physical Organic Chemistry
EPSRC Industrial Sector Classifications:	No relevance to Underpinning Sectors
Related Grants:
Panel History:	Panel Date Panel Name Outcome 17 Oct 2013 EPSRC Physical Sciences Chemistry - October 2013 Announced
Summary on Grant Application Form
The development of new catalytic reactions and the study of unusual reaction mechanisms is a fundamental part of science, crucial to drive the development of new chemical reactions. This essential field aims to enhance and refine our understanding of how chemical reactions work, not only to satisfy our curiosity about the world surrounding us, but also to help the synthetic and industrial chemists to rationalise results, predict outcomes and design better and more practical ways of creating new compounds by avoiding troublesome side reactions, identifying new transformations and devising safer reaction conditions. Activation of unsaturated bonds by transition metal complexes is a very useful tool to create new C-C and C-X (X = heteroatom) bonds in a very selective and efficient way. Although transition-metal catalysed reactions of alkenes and alkynes have been widely studied, the coordination chemistry of allenes (molecules with two consecutive carbon-carbon double bonds) has only started to be explored, being the reaction with nucleophiles one of the most important examples. Catalytic cycles involving allenes give the possibility of selective reactions towards one double bond or the other. The selection of the metal (Pd, Rh, Ir, Au, Pt) employed in the reaction is critical to control the outcome of the reaction, and different coordination modes have been proposed to explain the new reactivities encountered. In this project we propose a mechanistic approach to the study of a recently reported Pt-catalysed reaction of allenes and nucleophiles, and the use of the knowledge gained to discover new reactivities and unravel the synthetic potential behind the proposed key reaction intermediates to give complex structures that could be exploited as new drugs. Recent discoveries in our laboratory indicate that, under platinum-catalysed conditions, and in contrast to more conventional gold catalysis, the reaction of allenes and nucleophiles proceeds by a divergent mechanistic pathway involving a rare Pt-allene coordination, which allow the formation of new reaction products: double addition of the nucleophiles on to the terminal carbon of the allene and complete saturation of the second double bond of the allenic system occurs in the presence of platinum complexes, in contrast to the mono addition and formation of E-allylated products with other metals, like gold. We have already shown the applicability of this reaction for the synthesis of acetals and bisindolylalkanes, important products with varied biological activity. Understanding the main reaction pathway, the parameters of the individual steps, and identification of the possible intermediates involved in this catalytic cycle, are crucial for the control of the reaction, the discovery of new catalytic cycles and new one-pot multistep transformations derived from key intermediates of the reaction towards complex molecules that incorporate important structural motifs observed in natural products. We proposed an interactive approach were the knowledge gain form the mechanistic study will be use to exploit new reactivities and divergent catalytic cycles, and improved catalytsts will be design according to the needs of the new reactivities and the mechanistic information gathered. The work described in this proposal has the potential to influence science research in a broad sense, as it falls in a very multidisciplinary environment, and collaborations between all the chemistry disciplines and with industry will be exploited.
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