110718-81-5Relevant articles and documents
NEW ORGANOCOPPER REAGENTS PREPARED UTILIZING HIGHLY REACTIVE COPPER
Rieke, Reuben D.,Wehmeyer, Richard M.,Wu, Tse-Chong,Ebert, Greg W.
, p. 443 - 454 (1989)
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.
Direct Formation and Reaction of Thienyl-Based Organocopper Reagents
Rieke, Reuben D.,Klein, Walter R.,Wu, Tse-Chong
, p. 2492 - 2500 (2007/10/02)
The preparation of a highly reactive zerovalent copper complex by the direct reduction of lithium (2-thienylcyano)cuprate with preformed lithium naphthalenide is described.This active copper species oxidatively adds to carbon-halogen bonds to form organocopper reagents.The ability to directly form the organocopper reagent from organic halides and active copper allows for the incorporation of a wide variety of functionalities to be present in the organic halides and the organocopper reagents.Significantly, this formulation of active copper was able to oxidatively add to allyl chlorides and acetates at low temperatures to allow the direct formation of allylic organocopper reagents without Wurtz-type homocoupling.These functionalized organocopper compounds are able to undergo a variety of reactions, such as cross-coupling with acid chlorides, 1,4-conjugate addition with α,β-unsaturated carbonyl compounds, and intermolecular and intramolecular epoxide-opening reactions.Subsequently, this copper species avoids the use of phosphine ligands affording the product isolation much more convenient than with phosphine-based organocopper reagents.
Direct Formation of Functionalized Alkylcopper Reagents from Alkyl Halides Using Activated Copper. Conjugate Addition Reactions with 2-Cyclohexen-1-one
Wehmeyer, Richard M.,Rieke, Reuben D.
, p. 5056 - 5057 (2007/10/02)
Activated copper, prepared by the lithium naphthalide reduction of CuIPR3 complexes, has been shown to readily form stable alkylcopper compounds at low temperatures by direct insertion into carbon-halogen bonds.Alkylcopper reagents containing ester, nitrile, and chloride functionalities have been prepared directly from the corresponding alkyl bromides.These alkylcopper reagents have been used effectively in conjugate additions to 2-cyclohexen-1-one, giving functionalized 3-alkylcyclohexanones in good to excellent yields.This approach allows for functionality previously unavailable in organocopper and cuprate reagents.
