New Lithium Cuprates for the Promotion of Directed Organic Transformations

摘要: The use of bimetallic bases to effect highly stereoselective organic transformations via Directed ortho Metalation (DoM) is an important synthetic tool and requires thorough investigation maximise efficiency develop a mechanistic understanding. This thesis begins with discussion the history DoM covering firstly monometallic lithium before moving magnesiate, zincate, aluminate, manganate finally cuprate bases, which are focus this thesis. A description techniques employed in project, focuses on X-ray crystallography as primary characterisation tool, follows. experimental procedures associated data also presented. These demonstrate that addition 2 equivalents amido or phosphido copper(I) salt results crystallisation series bis(amido)and bis(phosphido)cuprates, phosphidocopper compounds, many suitable Cupration (DoCu) reagents. Syntheses involving ligands lead isolation only one species, Gilman-type [(Cy2P)2CuLi · 2THF], 11, forms polymer solid-state ineffective DoCu agent. Alternative pathways yield interesting novel compounds [(Ph2P)6Cu4][Li 4THF]2, 9, Ph2PCu(CN)Li 2THF, 10, investigated. structures all three species discussed detail. In situ preparations bis(amido)cuprate from CuCl shown be effective deprotocupration halopyridines. Reactions carried out without LiCl present mixture Lipshutz-type formulation active species. Analogous CuBr deprotonation although do not provide consistently high-yields. solid-state, both form cuprates, [(TMP)2Cu(X)Li2 THF]2 (X = Cl, Br). effects changing donor solvent weaker Lewis base diethyl ether syntheses cuprates investigated, resulting Et2O]2 CN, Hal). show solid-