Direct synthesis of nitroaryl acetylenes from acetylenes and nitroarenes via oxidative nucleophilic substitution of hydrogen.

Robert Bujok,Mieczysław Mąkosza

doi:10.1039/c6cc07475h

Abstract

Acetylenic carbanions add to nitroarenes (dinitrobenzenes, nitropyridines, etc.) to form σH-adducts that are subsequently oxidized by DDQ according to the oxidative nucleophilic substitution of hydrogen (ONSH) pathway to give nitroaryl acetylenes.

Highlights

Acetylenic carbanions add to nitroarenes to form rH-adducts that are subsequently oxidized by DDQ according to the oxidative nucleophilic substitution of hydrogen (ONSH) pathway to give nitroaryl acetylenes
Introduction of acetylenic substituents into aromatic rings is of great interest in modern organic synthesis, because the presence of such fragments adds interesting physicochemical properties[1] and because they can be converted into a variety of functionalities
All reported methods of introduction of acetylenic substituents into aromatic rings consist of replacement of halogens: transition metal catalyzed replacement of I, Br, and Cl by terminal acetylenes – Sonogashira reaction and SNAr of fluorine in fluoronitrobenzenes by acetylenic carbanions

Summary

Introduction

Acetylenic carbanions add to nitroarenes (dinitrobenzenes, nitropyridines, etc.) to form rH-adducts that are subsequently oxidized by DDQ according to the oxidative nucleophilic substitution of hydrogen (ONSH) pathway to give nitroaryl acetylenes. All reported methods of introduction of acetylenic substituents into aromatic rings consist of replacement of halogens: transition metal catalyzed replacement of I, Br, and Cl by terminal acetylenes – Sonogashira reaction and SNAr of fluorine in fluoronitrobenzenes by acetylenic carbanions.

Results

Conclusion