Halogen-Bond-Based Organocatalysis Unveiled: Computational Design and Mechanistic Insights

Abstract

Halogen-bond-based organocatalysis is a promising alternative to extensively explored hydrogen-bond-based catalysis. This paper presents a comprehensive theoretical investigation of the structural and electronic properties of the σ-hole, as well as the computational design of a series of electronically activated monodentate and bidentate iodine and benzimidazolium achiral donor systems, inspired by experimental and computational papers published in the past decade. The aforementioned activation modes are compared, and the mechanistic details of the reaction are discussed.