Copper organo derivatives

Organo Derivatives. Only in the Cu1 state does copper form Cu-C bonds the most stable are (/z5-C5H5)CuPR3, obtained by interaction of CuAfPR andTlCsHs.11... 

The reaction described is of considerable general utility for the preparation of benzoyloxy derivatives of unsaturated hydrocarbons.2"8 Reactions of 2-butyl perbenzoate with various other classes of compounds in the presence of catalytic amounts of copper ions produce benzoyloxy derivatives. Thus this reaction can also be used to effect one-step oxidation of saturated hydrocarbons,9, 10 esters,6,11 dialkyl and aryl alkyl ethers,12 14 benzylic ethers,11,15 cyclic ethers,13,16 straight-chain and benzylic sulfides,12, 17-19 cyclic sulfides,11,19 amides,11 and certain organo-silicon compounds.20... 

The three elements lithium, sodium, and potassium bear little resemblance to copper, silver, and gold in their inorganic derivatives but, with the exception of gold, they show more resemblance in their organo-metallic compounds. 

These methods of acylation are devices to solve the problem that acid chlorides and organo-lithium or magnesium derivatives are not good partners. To get good acylation with acid chlorides, as well as good alkylation with alkyl halides, we need to turn to other metals which provide softer carbanion complexes, less basic compounds with metals showing a lower affinity for oxygen. The most important is copper. 

An easy synthesis of prenyl naphthoquinones, e.g. menaquinone-2 (205 n = 2), was achieved by coupling the appropriate prenyl halide with an organo-copper derivative of the electrochemically derived quinone bisacetal (216). Menaquinone-2 and phylloquinone (204) were also obtained in good yields by reaction of 2-methyl-1,4-naphthoquinone (205 n =0) with geranyl and phytyl halides in the presence of metal dust. A one-step method for the preparation of vitamin K analogues uses cyclodextrin inclusion catalysts.Thus reaction of the diol (217) with allyl bromide in the presence of oxygen and/3-cyclodextrin at pH 9 afforded the menaquinone analogue (218). 

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