Radical chemistry of nitrosoarenes: concepts, synthetic applications and directions.

Nitrosoarenes are readily available and highly reactive, making them promising building blocks in organic chemistry. The recent development of radical conversions of nitrosoarenes provides an alternative and powerful platform for the facile construction of a wide range of sterically hindered secondary amines and high-value N-heterocycles that are difficult to obtain through other means. Accordingly, a great variety of radical transformations such as additions, cascade reactions by radical relay, and multi-component reactions of nitrosoarenes have been extensively developed. In this review, we aim to summarize the recent progress on the radical reactions of nitrosoarenes with special emphasis on the scope, limitations, and underlying working mechanism. Hopefully, this review will provide a useful guideline for researchers for further exploration of valuable radical transformations and applications of nitrosoarenes.

[1]  A. Gallo,et al.  Gold-Catalyzed Synthesis of 3-Arylindoles via Annulation of Nitrosoarenes and Alkynes , 2011 .

[2]  M. D. Hill,et al.  Applications of Fluorine in Medicinal Chemistry. , 2015, Journal of medicinal chemistry.

[3]  A. F. Voter,et al.  Synthesis of Macrocyclic Polymers Formed via Intramolecular Radical Trap-Assisted Atom Transfer Radical Coupling. , 2012, ACS macro letters.

[4]  Sandeep Patel,et al.  Nitrosoarene-catalyzed regioselective aromatic C-H sulfinylation with thiols under aerobic conditions. , 2020, Chemical communications.

[5]  S. Jockusch,et al.  The reaction of singlet oxygen with enecarbamates: a mechanistic playground for investigating chemoselectivity, stereoselectivity, and vibratioselectivity of photooxidations. , 2008, Accounts of chemical research.

[6]  Stephen P. Thomas,et al.  Amine-bis(phenolate) Iron(III)-Catalyzed Formal Hydroamination of Olefins. , 2016, Chemistry, an Asian journal.

[7]  D. MacMillan,et al.  Photoredox Catalysis in Organic Chemistry , 2016, The Journal of organic chemistry.

[8]  Thomas E. La Cruz,et al.  Practical olefin hydroamination with nitroarenes , 2015, Science.

[9]  Rai‐Shung Liu,et al.  Copper-Catalyzed Three-Component Annulations of Alkenes, Nitrosoarenes, and N-Hydroxyallylamines To Form Fused Oxazinane/Isoxazolidine Heterocycles. , 2017, Angewandte Chemie.

[10]  Xile Hu,et al.  Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides , 2016, Nature Communications.

[11]  Rai‐Shung Liu,et al.  [3 + 2]-Annulations of N-Hydroxy Allenylamines with Nitrosoarenes: One-Pot Synthesis of Substituted Indole Products. , 2016, Organic letters.

[12]  A. Mackor,et al.  C-nitroso compounds. Part III. Alkoxy-alkyl-nitroxides as intermediates in the reaction of alkoxy-radicals with nitroso compounds , 1967 .

[13]  A. Mackor,et al.  C-Nitroso compounds—VII , 1967 .

[14]  T. Kauffmann,et al.  Stable Free Radicals Formed by Addition of Sodium onto Aromatic Nitroso Compounds , 1963 .

[15]  N. G. Khaligh.  Recent Advances and Applications of tert-Butyl Nitrite (TBN) in Organic Synthesis , 2020, Mini-Reviews in Organic Chemistry.

[16]  Peter R Ogilby,et al.  Singlet oxygen: there is indeed something new under the sun. , 2010, Chemical Society reviews.

[17]  P. Navarrete-Encina,et al.  Nitrosobenzene: electrochemical, UV-visible and EPR spectroscopic studies on the nitrosobenzene free radical generation and its interaction with glutathione , 2000 .

[18]  Marvin J Miller,et al.  Nitroso Diels-Alder (NDA) reaction as an efficient tool for the functionalization of diene-containing natural products. , 2014, Organic & biomolecular chemistry.

[19]  Shifa Zhu,et al.  Domino Reaction between Nitrosoarenes and Ynenones for Catalyst-Free Preparation of Indanone-Fused Tetrahydroisoxazoles. , 2019, Organic letters.

[20]  P. Zuman,et al.  Addition, Reduction, and Oxidation Reactions of Nitrosobenzene , 1994 .

[21]  B. Tan,et al.  Asymmetric Construction of Spirooxindoles by Organocatalytic Multicomponent Reactions Using Diazooxindoles. , 2015, Angewandte Chemie.

[22]  J. Kang,et al.  Conversion of nitrosobenzenes to isoxazolidines: an efficient cascade process utilizing reactive nitrone intermediates. , 2008, Chemical communications.

[23]  L. Deng,et al.  Isolable Anion Radicals of Nitrosoarenes , 2020 .

[24]  M. Hriberšek,et al.  N-Trifluoromethylation of Nitrosoarenes with Sodium Triflinate. , 2017, Organic letters.

[25]  C. Tung,et al.  Iron-Catalyzed Reductive Coupling of Nitroarenes with Olefins: Intermediate of Iron–Nitroso Complex , 2020 .

[26]  Angela van der Werf,et al.  Synthesis of Fluorinated Amide Derivatives via a Radical N-Perfluoroalkylation–Defluorination Pathway , 2020, Organic letters.

[27]  David J. Fisher,et al.  Synthesis of Hindered Anilines: Three-Component Coupling of Arylboronic Acids, tert-Butyl Nitrite, and Alkyl Bromides. , 2016, Organic letters.

[28]  A. Caselli,et al.  Synthesis of indoles by intermolecular cyclization of unfunctionalized nitroarenes and alkynes, catalyzed by palladium-phenanthroline complexes. , 2006, The Journal of organic chemistry.

[29]  Marvin J Miller,et al.  The nitrosocarbonyl hetero-Diels-Alder reaction as a useful tool for organic syntheses. , 2011, Angewandte Chemie.

[30]  E. Tillman,et al.  Dimerization of Poly(methyl methacrylate) Chains Using Radical Trap-Assisted Atom Transfer Radical Coupling , 2014 .

[31]  David J. Fisher,et al.  Synthesis of Hindered α-Amino Carbonyls: Copper-Catalyzed Radical Addition with Nitroso Compounds. , 2015, Journal of the American Chemical Society.

[32]  A. Mackor,et al.  C-nitroso compounds—II : On the photochemical and thermal formation of nitroxides from nitroso compounds, as studied by E.S.R. , 1967 .

[33]  A. R. Forrester,et al.  Nitrosocarbonylbenzene as a spin trap , 1984 .

[34]  A. M. Tafesh,et al.  A Review of the Selective Catalytic Reduction of Aromatic Nitro Compounds into Aromatic Amines, Isocyanates, Carbamates, and Ureas Using CO. , 1996, Chemical reviews.

[35]  Soumen Ghosh,et al.  EDA complex directed N-centred radical generation from nitrosoarenes: a divergent synthetic approach. , 2019, Chemical communications.

[36]  Rai‐Shung Liu,et al.  Copper-Mediated [3+2] Annulation of 3-N-Hydroxyallylamines with Nitrosoarenes. , 2016, Chemistry.

[37]  C. Stephenson,et al.  Shining light on photoredox catalysis: theory and synthetic applications. , 2012, The Journal of organic chemistry.

[38]  F. Ragaini,et al.  Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes , 2019, ChemCatChem.

[39]  D. Leonori,et al.  Photoredox Synthesis of Arylhydroxylamines from Carboxylic Acids and Nitrosoarenes , 2018, Synthesis.

[40]  Jie Wu,et al.  Nitrosoarenes as Nitrogen Source for Generation of Sulfonamides with the Insertion of Sulfur Dioxide under Metal‐Free Conditions † , 2020 .

[41]  W. Xiao,et al.  [3 + 2]-Cycloaddition of 2 H-Azirines with Nitrosoarenes: Visible-Light-Promoted Synthesis of 2,5-Dihydro-1,2,4-oxadiazoles. , 2019, Organic letters.

[42]  Wei Zhu,et al.  Next Generation of Fluorine-Containing Pharmaceuticals, Compounds Currently in Phase II-III Clinical Trials of Major Pharmaceutical Companies: New Structural Trends and Therapeutic Areas. , 2016, Chemical reviews.

[43]  Chang-Liang Sun,et al.  Transition-metal-free coupling reactions. , 2014, Chemical reviews.

[44]  W. Adam,et al.  The nitroso ene reaction: a regioselective and stereoselective allylic nitrogen functionalization of mechanistic delight and synthetic potential. , 2003, Chemical reviews.

[45]  Andrew G. Leach,et al.  Diels-Alder and ene reactions of singlet oxygen, nitroso compounds and triazolinediones: transition states and mechanisms from contemporary theory. , 2002, Chemical communications.

[46]  Rai‐Shung Liu,et al.  Stereoselective annulation between an allene, an alkene, and two nitrosoarenes to access bis(isoxazoliodine) derivatives. , 2017, Organic & biomolecular chemistry.

[47]  Stephen P. Thomas,et al.  Chemoselective nitro reduction and hydroamination using a single iron catalyst† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc04471e , 2016, Chemical science.

[48]  Hisashi Yamamoto,et al.  Rich chemistry of nitroso compounds. , 2005, Chemical communications.

[49]  P. Baran,et al.  Radicals: Reactive Intermediates with Translational Potential , 2016, Journal of the American Chemical Society.

[50]  B. Patel,et al.  tert ‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis , 2019, Chemistry – An Asian Journal.

[51]  K. Houk,et al.  On the mechanism of nitrosoarene-alkyne cycloaddition. , 2009, Journal of the American Chemical Society.