Halotrimethylsilane-Nitrite/Nitrate Salts: Efficient and Versatile Reagent System for Diverse Organic Synthetic Transformations

Abstract

The reagent system comprised of halotrimethylsilane and nitrite or nitrate salts has now been successfully used as an efficient system for a series of versatile synthetic transformations. In recent years, the significance and efficacy of this system for reactions such as nitration of aromatics and olefins, oxidation of thiols to sulfonyl chlorides, ipso-nitrosation/nitration of arylboronic acids, ipso-nitration of α,β-unsaturated carboxylic acids to nitro olefins, etc. have been disclosed. Though the reagent system has not been exploited to its full potential, the reported reactions reveal its advantages as a very safe and convenient system that works under mild conditions. This brief Account reveals various synthetic applications of halotrimethylsilane-nitrite/nitrate salts in organic synthesis hitherto reported.1 Introduction2 Reactions Using a Halotrimethylsilane-Nitrate Salt System2.1 Nitration of Olefins and Aromatics2.2 One-Pot Preparation of gem-Chloronitroso, gem-Chloronitro, and vic-Dichloro Compounds2.3 One-Step Conversion of Anilines into Haloarenes2.4 Deoximation of Aldoximes to Aldehydes and Ketoximes to ­Ketones2.5 One-Pot Synthesis of Cyclic/Noncyclic α-Nitroketones from ­Cyclic/Noncyclic Olefins2.6 ipso-Nitration of Arylboronic Acids2.7 ipso-Nitrosation of Arylboronic Acids2.8 Oxidation of Sulfides and Sulfoxides to Sulfones2.9 Oxidative Chlorination of Thiols and Disulfides to Sulfonyl ­Chlorides2.10 α-Halogenation of Carbonyl Compounds2.11 Decarboxylative ipso-Nitration and Dibromination of Cinnamic Acid3 Conclusion