New Organocopper Reagents Prepared Utilizing Highly Reactive Copper.

Abstract Highly reactive copper solutions have been prepared by the lithium naphthalide reduction of copper(I) iodide/trialkylphosphine complexes. These activated copper solutions will react with organic halides under very mild conditions to form stable organocopper reagents. Significantly, the organocopper reagents can contain considerable functionalities such as ester, nitrile, chloride, epoxide, and ketone groups. These functionalized organocopper species undergo many reactions typical of other organocopper species. Intermolecular 1,4-additions, epoxide-opening reactions, and ketone formation with acid chlorides have been successfully achieved. In addition, this methodology has been applied to an intramolecular epoxide-cleavage reaction. The Influence of the connecting chain length, substitution pattern, reaction solvent, and CuI/phosphine complex upon the regioselectivity of the intramolecular cyclization is described.