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

Halogen-bond-based organocatalysis is a promising alternative to the extensively explored halogen-bond-based catalysis. This paper presents a comprehensive theoreti- cal 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 com- putational papers published in the last decade. The aforementioned activation modes are compared, and the mechanistic details of the reaction are discussed.