Rational Optimization of Lewis‐Acid Catalysts for the Direct Amination of Alcohols, Part 1 – Activity Descriptors for Metal Triflates and Triflimides

Abstract

Herein we report a comparison of Lewis acidity indicators (affinity scales, electronegativity, Fukui functions, global electrophilicity index) with a new in silico Beckett–Childs descriptor based on the build‐up of partial charge, computed by DFT, on phosphine oxide coordinated to a Lewis acid. When applied to a broad series of triflate and triflimide salts, the last descriptor allowed a qualitative description of catalytic activity trends for the model amination reaction of benzyl alcohol with aniline. A high activity for titanium triflimide was predicted and experimentally confirmed.