The reaction of alkylcopper(I) complexes with carbon monoxide: a new ketone synthesis

✍ Scribed by Jeffrey Schwartz

• Publisher: Elsevier Science
• Year: 1972
• Tongue: French
• Weight: 204 KB
• Volume: 13
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)84940-6

✦ Synopsis

The use of alkylcopper(I) "ate" complexes for alkylation of a wide variety of organic substrates continues to be a subject of active interest. 192 In this context, we wish to report our observations concerning the reaction of several of such complexes with carbon monoxide, a reaction which, under appropriate conditions , results in high yields of synewtrically substituted ketones. These studies have shown that while lithium di-n-butylcuprate (I.;) absorbs one equivalent of carbon monoxide (based on starting millimoles of copper) to give 5-nonanone in 70% yield upon hydrolysis, butylcopper(1) (2_) yields no ketone on similar treatment with carbon monoxide. We also note that q-butyl(tri-n-butylphosphine)copper(I) (z), in ether, absorbs one equivalent of carbon monoxide but yields 5-nonanone on hydrolysis only when lithium halide is present in the reaction mixture (Eq. 1). When lithium iodide is removed by precipitation with dioxane, 3 tri-g-butylphosphine butylcopper(I) complex (2) does absorb