Copper Organometallics Research Articles

ChemInform Abstract: Synthesis and Reactivity of Open‐Chain and Cyclic 2‐Cyano Zinc and Copper Organometallics.

Abstract Various open-chain and cyclic β-cyano zinc and copper organometallics can be prepared by the reaction of the corresponding organic halides with zinc and subsequent transmetalation with CuCN · 2 LiCl. They react in fair to good yields with various organic electrophiles (enones, allylic bromides and benzoyl chloride) affording highly functionalized nitriles. High diastereoselectivities have been observed in coupling reactions with the cyclic 2-cyano organocopper derivatives. The x-ray structure of cyanoethylzinc iodide is also reported.

Preparation of functionalized zinc and copper organometallics containing sulfur functionalities at the alpha or gamma position

α-Chloroalkyl phenyl sulfides 1 readily insert zinc in THF at 25 °C (0.5–2 h), affording sulfur stabilized organozinc derivatives of type 2. The presence of a functional group such as an ester or a cyano group is tolerated in these organometallics. After a transmetallation to the corresponding copper reagent 3, they react with a wide range of electrophiles. Zinc and copper organometallics bearing a thiophenyl or a phenylsulfinyl group at the γ-position have also been prepared showing the generality of our approach.

A new preparation of highly functionaized aromatic and heteroaromatic zinc and copper organometallics

Functionalized aromatic iodides possessing an ester, cyano, chloride or keto group can be converted to arylzinc iodides by reaction with zinc in DMF or DMAC. After transmetallation to the corresponding arylcopper, they react with several electrophiles such as enongs, allylic halides and benzoyl chloride to afford highly functionalized aromatic compounds. Extension to the preparation of polyfunctionalized heteroaromatic zinc iodides and to an alkenylzinc iodide was also successful, although the zinc insertion to a pure (E)-alkenyl iodide furnished an E/Z mixture of alkenyl zinc iodides.

Synthesis and reactivity of open-chain and cyclic 2-cyano zinc and copper organometallics

Various open-chain and cyclic β-cyano zinc and copper organometallics can be prepared by the reaction of the corresponding organic halides with zinc and subsequent transmetalation with CuCN · 2 LiCl. They react in fair to good yields with various organic electrophiles (enones, allylic bromides and benzoyl chloride) affording highly functionalized nitriles. High diastereoselectivities have been observed in coupling reactions with the cyclic 2-cyano organocopper derivatives. The x-ray structure of cyanoethylzinc iodide is also reported.

Rapid determination of zinc, copper and cadmium organometallics in mussels by gel-permeation high pressure liquid chromatography and in-line detection by inductively coupled plasma atomic emission spectrometry

Rapid determination of zinc, copper and cadmium organometallics in mussels by gel-permeation high pressure liquid chromatography and in-line detection by inductively coupled plasma atomic emission spectrometry