Transition-Metal-Free C-Vinylation of Ketones with Acetylenes: A Quantum-Chemical Rationalization of Similarities and Differences in Catalysis by Superbases MOH/DMSO and tBuOM/DMSO (M = Na, K)

Vladimir B Orel; Nadezhda M Vitkovskaya; Vladimir B Kobychev; Boris A Trofimov

doi:10.1021/acs.joc.8b00071

Transition-Metal-Free C-Vinylation of Ketones with Acetylenes: A Quantum-Chemical Rationalization of Similarities and Differences in Catalysis by Superbases MOH/DMSO and tBuOM/DMSO (M = Na, K)

J Org Chem. 2018 Apr 6;83(7):3719-3726. doi: 10.1021/acs.joc.8b00071. Epub 2018 Mar 14.

Authors

Vladimir B Orel^{1

2}, Nadezhda M Vitkovskaya¹, Vladimir B Kobychev¹, Boris A Trofimov²

Affiliations

¹ Laboratory of Quantum Chemistry , Irkutsk State University , 1 K. Marks Street , 664003 Irkutsk , Russian Federation.
² A. E. Favorsky Irkutsk Institute of Chemistry , Siberian Branch of the Russian Academy of Sciences , 1 Favorsky Street , 664033 Irkutsk , Russian Federation.

PMID: 29505724
DOI: 10.1021/acs.joc.8b00071

Abstract

Transition-metal-free C-vinylation of acetone with phenylacetylene catalyzed by superbases MOH/DMSO and tBuOM/DMSO (M = Na, K) has been theoretically evaluated in the B3LYP/6-311++G**//B3LYP/6-31+G* approach to rationalize similarities and differences in activity of the above catalytic systems. The close solvate surroundings of sodium and potassium tert-butoxides have been studied. Formation of tBuOM· nDMSO complexes and their structure and thermodynamic stability are discussed in comparison with similar complexes of alkali-metal hydroxides MOH· nDMSO. Activation barriers of the title reaction in the presence of tBuOM· nDMSO complexes are found to be less than those with MOH· nDMSO complexes participating.

Publication types

Research Support, Non-U.S. Gov't