Organic Nitrating Reagents

Abstract

Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of the first nitrating reactions in the 19th century, progress in this field has been constant. Yet, for many years the classical electrophilic nitration approach using a mixture of strong mineral acids dominated the field. However, in recent decades, the attention of researchers has focused on new reactivity and new reagents that can provide access to nitro compounds in a practical and straightforward way under mild reaction conditions. Organic nitrating reagents have played a special role in this field since they have enhanced reactivity. They also allow nitration to be carried out in an ecofriendly and sustainable manner. This review examines the development and application of organic nitrating reagents.1 Introduction2 Organic Nitrating Reagents2.1 Alkyl Nitrites2.2 Nitroalkanes2.3 Alkyl Nitrates2.4 N-Nitroamides2.5 N-Nitropyrazole2.6 N-Nitropyridinium Salts3 Organic Nitrating Reagents Generated In Situ3.1 Acyl Nitrates3.2 Trimethylsilyl Nitrate3.3 Nitro Onium Salts4 Organic Nitronium Salts5 Organic Nitrates and Nitrites5.1 Ammonium Nitrates5.2 Heteroarylium Nitrates5.3 Other Organic Nitrates5.4 Organic Nitrites6 Conclusion and Outlook

Photoredox Activation of Anhydrides for the Solvent‐Controlled Switchable Synthesis of gem‐Difluoro Compounds**

“…Another powerful platform for increasing molecular complexity is the use of functional group transfer reagents (FGTRs). [ 23 , 24 ] This strategy is based on the development of organic and inorganic reagents, which have the capacity to enforce the transfer of the desired functional group (FG) to a molecule in a straightforward fashion. The field of fluorine chemistry is one of the privileged examples,[ 25 , 26 ] which has advanced from the discovery of teflon and freon [27] to an extremely fertile bench of novel functionalities, reagents, and reactivities, such as fluoroalkylation, [28] sulfur‐based fluorination, [29] acyl fluorides chemistry, [30] etc.…”

Solvent-Controlled Switchable Synthesis of gem-Difluoro Compounds from Anhydrides under Photoredox Catalysis

“…Further substrate expansion to crucial functional groups was also examined to obtain the corresponding lactams and lactones with fluorinated ether (21), amide (22,53), ester (23), and ethers (39, 40) moiety. β-Substituted styrenes with phenyl (24), methyl (25,52), and oxazolidine (53) underwent the desired transformation successfully, giving the corresponding cyclic adducts in decent yields and very high diastereoselectivity (>99:1). The structures of lactams 1 and 24 were demonstrated by X-ray crystallography.…”

“…22 Another powerful platform for increasing the molecular complexity can be realized through the use of functional group transfer reagents (FGTRs). 23,24 This strategy is based on the development of organic and inorganic reagents with substantial reactivity, which have the capacity to enforce the transfer of the target functional group (FG) to a molecule in a straightforward fashion. The field of fluorine chemistry is one of the privileged examples, 25,26 which has advanced from the ՛՛chemistry՛՛ of teflon and freon 27 to an extremely fertile bench of novel functionalities, reagents, and reactivities, such as fluoroalkylation, 28 sulfur-based fluorination, 29 acyl fluorides chemistry, 30 etc.…”

Photoredox Activation of Anhydrides for the Solvent‐Controlled Switchable Synthesis of gem‐Difluoro Compounds**

“…Another powerful platform for increasing molecular complexity is the use of functional group transfer reagents (FGTRs) [23, 24] . This strategy is based on the development of organic and inorganic reagents, which have the capacity to enforce the transfer of the desired functional group (FG) to a molecule in a straightforward fashion.…”

“…[22] Another powerful platform for increasing molecular complexity is the use of functional group transfer reagents (FGTRs). [23,24] This strategy is based on the development of organic and inorganic reagents, which have the capacity to enforce the transfer of the desired functional group (FG) to a molecule in a straightforward fashion. The field of fluorine chemistry is one of the privileged examples, [25,26] which has advanced from the discovery of teflon and freon [27] to an extremely fertile bench of novel functionalities, reagents, and reactivities, such as fluoroalkylation, [28] sulfur-based fluorination, [29] acyl fluorides chemistry, [30] etc.…”