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Title: Water-tolerant organometallic reactions : nucleophilic additions to carbonyl compounds using allyl metals in aqueous solution
Author: Lock, S. J.
Awarding Body: University of Wales Swansea
Current Institution: Swansea University
Date of Award: 2003
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Against a background of the reactivity of traditional organometallics, this work describes nucleophilic addition reactions that take place via the intervention of metals in the presence of water. The experimental work focuses on allylation of aldehydes in water-containing solvents using nickel, bismuth and aluminium. Chapter 1 outlines the current influence of environmental issues on the practice of chemistry and the value of water as a solvent. Carbon-carbon bond formation is discussed in the context of mechanism and common methods are reviewed, particularly with respect to reaction of the carbonyl functional group. A sample of the well-established organometallic reagents are examined in terms of their characteristics and general reactivity, which then serve as a backdrop to a description of the types of metal-mediated reactions that occur in aqueous solutions. Chapter 2 describes allylation reactions using water-tolerant allylic metals species obtained via transmetallation between metal salts and allylic Grignard reagent. The properties and reactions of a nickel-containing allylating agent are examined in greater detail. Chapter 3 describes bismuth-mediated reactions in which zero-valent bismuth is generated in situ from a bismuth salt and a reducing metal in entirely aqueous solution. Chapter 4 examines the potential of using aluminium to promote allylation reactions in aqueous solutions. Chapter 5 focuses on allylations using bismuth powder in entirely aqueous solutions and the influences of a variety of additives. The scope and mechanism of reactions performed in potassium fluoride solution are explored in more detail.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available