Computational and mechanistic studies of the acylation of cyclopropanes

Gérard Audran , Paul Brémond , Sylvain R.A. Marque (1) , Didier Siri , Maurice Santelli

1 ICR - Institut de Chimie Radicalaire

As the well known protonated cyclopropanes' present calculations confirm the existence of acetylated cyclopropanes, we describe the structure of edge- and corner-acetylated cyclopropanes rising from the energetically favored addition of acetyl cation to cyclopropanes. Some of those explain the few available experimental results concerning the acetylation reaction of cyclopropanes. Structures have been calculated at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels of theory in ideal gas and in dichloromethane as solvent. Transition state geometries in ideal gas and in dichloromethane as solvent were confirmed by intrinsic reaction coordinate (IRC) calculations. (C) 2016 Elsevier Ltd. All rights reserved.

Keywords: Cyclopropanes; Acylation; Acetylated cyclopropanes; Transition state; Intrinsic reaction coordinate (IRC) calculations

Domains: Chemical Sciences

Gérard Audran, Paul Brémond, Sylvain R.A. Marque, Didier Siri, Maurice Santelli. Computational and mechanistic studies of the acylation of cyclopropanes. Tetrahedron Letters, 2016, 57 (16), pp.1743-1749. ⟨10.1016/j.tetlet.2016.03.012⟩. ⟨hal-01406678⟩