Origin of the regioselectivity in an intramolecular nucleophilic addition to arene chromium tricarbonyl complexes

The source of the regioselectivity in the intramolecular nucleophilic addition of nitrile-stabilized carbanions to arene chromium tricarbonyl complexes was investigated for seven different substitution patterns on the arenes. All of the arenes are 1,4-dioxygenated and the substitution varies in the oxygen substituent and in the substituents of the arene carbons (hydrogen and alkyl). The regioselectivity is correlated with the preferred conformations of the chromium tricarbonyl group which in turn was determined by solution and solid-state 13C NMR spectroscopy, 1H NMR spectroscopy in solution as well as X-ray diffraction. In the four complexes analyzed by X-ray diffraction and the three complexes analyzed by solid-state 13C NMR spectroscopy, there was only one complex where it was found that the preferred conformation of the –Cr(CO)3 is different in solution than it is in the solid-state.

Graphical abstractThe regioselectivity for intramolecular nucleophilic addition to arene chromium tricarbonyl complexes is correlated with the positions of the carbon monoxide ligands in the solid state to the changes in the chemical shifts of the arene carbons in the solid state and to the changes in the chemical shifts of the arene carbons in solution.Figure optionsDownload full-size imageDownload as PowerPoint slide