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THE ACTIVATION AND SELECTED ORGANOMETALLIC CHEMISTRY OF COPPER (ORGANOCOPPER, ORGANOCUPRATE, ULLMANN, COUPLING, CROSS-COUPLING)
Abstract
A method has been developed for producing a highly activated zero-valent copper of sufficient reactivity to allow direct oxidative addition of most organic halides to produce organocopper reagents. These reagents undergo most of the substitution chemistry known for organocuprate compounds. This methodology allows the incorporation of functionality into these reagents which is prohibited when the traditional lithium and Grignard precursors are used. The activated copper is produced by mixing, under an atmosphere of argon, an ethereal solution of CuI(.)P(Et)(,3) with an equivalence of a cooled, preformed, ethereal solution of lithium napthalide. The resultant zero-valent copper is then used in subsequent reactions. Alkyl, alkenyl, alkynyl, and aryl halides all react in high yields. The alkylcopper compounds are not stable under the conditions of reaction and further react to give elimination, reduction, and homocoupled products in good yields. The alkenyl, alkynyl, and aryl halides react to produce stable intermediates which can be isolated or reacted with other reagents. Functionality such as -CN, and -NO(,2) has been incorporated into these compounds. These stable organocuprate reagents have been cross-coupled with acid chlorides to form the corresponding ketones, and with alkyl halides to form the corresponding coupled products in high yields.
Subject Area
Organic chemistry
Recommended Citation
EBERT, GREGORY WAYNE, "THE ACTIVATION AND SELECTED ORGANOMETALLIC CHEMISTRY OF COPPER (ORGANOCOPPER, ORGANOCUPRATE, ULLMANN, COUPLING, CROSS-COUPLING)" (1985). ETD collection for University of Nebraska-Lincoln. AAI8526618.
https://digitalcommons.unl.edu/dissertations/AAI8526618