Multi-faceted reactivity of N-fluorobenzenesulfonimide (NFSI) under mechanochemical conditions: fluorination, fluorodemethylation, sulfonylation, and amidation reactions.

José G Hernández,Dajana Barišić,Hervé Geneste,Karen J Ardila-Fierro

doi:10.3762/bjoc.18.20

José G Hernández, Dajana Barišić + Show 2 more

Open Access

https://doi.org/10.3762/bjoc.18.20

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Abstract

In the search for versatile reagents compatible with mechanochemical techniques, in this work we studied the reactivity of N-fluorobenzenesulfonimide (NFSI) by ball milling. We corroborated that, by mechanochemistry, NFSI can engage in a variety of reactions such as fluorinations, fluorodemethylations, sulfonylations, and amidations. In comparison to the protocols reported in solution, the mechanochemical reactions were accomplished in the absence of solvents, in short reaction times, and in yields comparable to or higher than their solvent-based counterparts.

Highlights

Mechanosynthesis of organic molecules and materials using mechanochemical techniques such as ball milling, extrusion, grinding, etc. [1,2,3] have enabled the development of known and new chemical transformations in a more sustainable fashion [4]
By mechanochemistry, NFSI can engage in a variety of reactions such as fluorinations, fluorodemethylations, sulfonylations, and amidations
We focused on the reaction between arenes 1a–c and NFSI by ball milling in the absence of external heating (Scheme 2a)

Summary

Introduction

Mechanosynthesis of organic molecules and materials using mechanochemical techniques such as ball milling, extrusion, grinding, etc. [1,2,3] have enabled the development of known and new chemical transformations in a more sustainable fashion [4]. Formation of 2c'' from 1,3,5-trimethoxybenzene (1c) requires a fluorodemethylation pathway to be operational under the ball-milling conditions, for example through the reaction of product 2c with the second equivalent of NFSI.

Results

Conclusion