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Title: Heterobimetallic bases in deprotonative metallation
Author: Haywood, J.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2010
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The work presented in this thesis makes use of the fact that treatment of a copper(I) salt with 2 eq. of an amido or alkyl lithium allows isolation of bisamido- and alkylamido cuprates. These, along with the alumina reagent also discussed, have been shown to be active in the directed ortho metallation (DoM) of a wide range of functionalised aromatics, a synthetically useful reaction. Chapter 4 looks at the solid-state structures of a range of reagents including TMP2CuLi2(CN).THF (TMP = 2,2,6,6-tetramethylpiperidido) and MeCuTMPLi-TMEDA (TMEDA = tetramethylethelene diamine). Investigation has shown that the presence of two amido groups, both capable of forming strong inter-metal bridges, leads to Lipshutz-type structures in donor solvent. In contrast, the presence of a copper-bound alkyl group leads to Gilman-type reagent formation due to poor bridging ability. The effect of the lithium-bridging anion in the Lipshutz form is also investigated, with isolation of TMP2CuLi2(I).THF and (TMP2CuLi)2 showing the importance of solvent effects. Chapter 5 presents solution state date from both theoretical and experimental directions. The theoretical data suggest that the reactivity of the discussed cuprate reagents is controlled by a complex set of equilibria with both Gilman- and Lipshutz-type species present in solution. These equilibria are found to depend on the presence and identity of the copper-lithium bridging groups. Chapter 6 moves away from copper-based systems, looking at solution-state data collected on aluminate reagent. AliBu3LiTMP.THF. Chapter 7 presents ideas for further work, and the rationale behind them.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available