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Advancements in active copper chemistry
Abstract
The Rieke method of metal activation has been employed to generate new forms of highly reactive copper which can be used to form organocopper reagents directly from the corresponding organic halides. The low temperature reduction of CuI$\cdot$PR$\sb3$ and CuCN$\cdot$nLiX complexes with lithium naphthalenide resulted in the formation of highly reactive copper species which underwent oxidative addition to a variety of functionalized alkyl bromides, aryl bromides, and aryl iodides to form the corresponding organocopper reagents. These organocopper reagents reacted with a variety of electrophiles conducive to cuprate chemistry. The development of CuCN$\cdot$nLiX-based active copper has allowed for facile separation of products, free from phosphine contamination. The active copper derived from CuCN$\cdot$nLiX complexes also reacted with allyl chlorides to form allyl copper reagents directly without significant homocoupling. These allyl copper reagents contained a wide range of electrophilic functional groups and reacted cleanly with various carbonyl electrophiles in high yield. The reaction of active copper with 2,3-dichloropropene resulted in a new bis-copper reagent which underwent two successive couplings with two different electrophiles in a one-pot procedure. The two equivalent reduction of Cu(I) complexes has lead to the formation of a formal copper anion. The copper anion reacts at low temperatures with alkyl, aryl, and allylic halides to form the corresponding organocopper compound. The copper anion has also been used to form higher order allylcyanocuprates as well as "non-ate" allyl organocopper species.
Subject Area
Organic chemistry
Recommended Citation
Stack, Douglas E, "Advancements in active copper chemistry" (1993). ETD collection for University of Nebraska-Lincoln. AAI9331430.
https://digitalcommons.unl.edu/dissertations/AAI9331430