New Theoretical Concepts for Understanding Organic Reactions Held in Sant Feliu de Guixols (Spain) on 19 June - 2 July 1988

摘要

Little is known experimentally about the detailed mechanisms of organolithium reactions, which are so commonly used for synthetic purposes. Theoretical calculations can make a real contribution to mechanistic chemistry, since the structures and energies of transition states can be calculated and characterized. We have examined several model reactions including the addition HLi, CH3Li, and their respective dimers to be multiply bonded systems, e.g., formaldehyde, ethylene, and acetylene. These reactions proceed stepwise, and are initiated by complex formation between the lithium compound and the substrate. The transition structures which follow require little activation energy, and the bond lengths are little changed from those of the initial complexes. (jes)