Cleavage of acetylenic substituents from camphor-derivatives by copper(I) chloride

Copper(I) chloride was found to be a highly efficient reagent to promote the cleavage of acetylenic substituents from the camphor skeleton of compounds 1 containing two C–C triple bonds as well as from the compounds 6 and 7 containing one. This is a formal reversal of the formation of these compounds by the reaction of acetylides with keto and imino groups in compound 18. The substituent R at the triple bond modifies the reactivity and regioselectivity. As intermediates in the process we identified complexes of the types [Cu(L)depr] (where (L)depr denotes a deprotonated camphor-derived ligand (L)) and [CuCl(L)]. Quantum mechanical calculations support and rationalize the experimental results.

Graphical abstractCuCl selectively cuts the acetylenic substituents from the camphor skeleton in a reaction that is a formal reversal of the formation of the camphor-derived alkyne compounds. Calculations on model systems show possible intermediates and reaction paths.Figure optionsDownload full-size imageDownload as PowerPoint slide