N-Nitroheterocycles: Bench-Stable Organic Reagents for Catalytic Ipso-Nitration of Aryl- and Heteroarylboronic Acids

Abstract

Photocatalytic and metal-free protocols to access various aromatic and heteroaromatic nitro compounds through ipso-nitration of readily available boronic acid derivatives were developed using non-metal-based, bench-stable, and recyclable nitrating reagents. These methods are operationally simple, mild, regioselective, and possess excellent functional group compatibility, delivering desired products in up to 99% yield.

Application of [PVI-SO3H]NO3 as a novel polymeric nitrating agent with ionic tags in preparation of high-energetic materials

“…10,11 Architecture of novel renewable and sustainable nitrating reagent in the organic transformation has attracted much attention in the science and industry because of their unique properties, such as efficiency, reusability, reactivity, stability, selectivity, generality and easy separation of the catalyst. [12][13][14][15][16][17][18] These methods of preparation of energetic materials were previously reported in the presence of some various nitrating agents, co-catalysts, and solvents, mixed acid of concentrated nitric acid and sulfuric acid, high temperature, long reaction times, and low yields [19][20][21][22][23][24][25][26][27][28][29][30] (Scheme 1).…”

Fluorinated Aryl Boronates as Building Blocks in Organic Synthesis

“…Nitroaromatic compounds are highly useful synthons in pharmaceutical chemistry [96] . Although no examples of the conversion of aryl boronate esters into their nitroaromatic counterparts have been reported, these useful compounds can be prepared using aryl boronic acids [97] or trifluoroborate salts [98] . Recently, Katayev et al .…”

“…Recently, Katayev et al . reported the conversion of aryl boronic acids into their nitro analogues using non‐metal, recyclable, and bench‐stable nitrating reagents, such as N ‐nitrosaccharin [97] . N ‐Nitrosaccharin was readily synthesized from the reaction of a saccharin solution in acetic anhydride with nitric acid (Scheme 43).…”

Synthesis, Characterization, and Reactivity of a Hypervalent‐Iodine‐Based Nitrooxylating Reagent

“…Evidently,abench-stable reagent that behaves as ac onvenient source of the NO 3 group and is amenable to direct CÀ Hn itrooxylation of ab road range of substrates under mild conditions,w hile avoiding the use of prefunctionalized starting materials or strong oxidants,r emains synthetically desirable,a nd essential to facilitate the development of new classes of organic nitrates with unexplored properties.Inview of our groupsi nterest in CÀHn itration [23] and hypervalent iodine chemistry, [24] we envisaged that the merger of the nitrooxy functional group with ah ypervalent iodine scaffold would provide ap latform for the development of such ar eagent. Hypervalent iodine benziodoxole and benziodoxolone reagents have emerged as powerful tools for oxidative functional group installation, and are generally considered as environmentally benign and widely available alternatives to traditional transition-metal-based reagents.…”