A Systematic Evaluation of the N-F Bond Strength of Electrophilic N-F Reagents: Hints for Atomic Fluorine Donating Ability

J Org Chem. 2017 Apr 21;82(8):4129-4135. doi: 10.1021/acs.joc.7b00036. Epub 2017 Apr 3.

Abstract

The recent discovery of the radical reactivity of a few traditionally electrophilic N-F reagents has sparked a renaissance of radical fluorination. A knowledge of the N-F bond dissociation enthalpies (BDE) of electrophilic N-F reagents is essential for understanding of their reactivities. However, a thorough literature survey revealed that such information is extremely sparse. This prompted us to carry out the first systematic computation on the N-F BDEs of electrophilic N-F reagents. The calculated N-F BDE scale of 88 electrophilic N-F reagents ranges from 49.3 to 80.0 kcal mol-1 in acetonitrile. The large variety of N-F reagents and wide span of N-F BDEs make the scale a useful tool not only for the future rational design of novel reagents but also for judicious selection of appropriate ones to explore new radical fluorinations.

Publication types

  • Research Support, Non-U.S. Gov't