Dual roles of sulfonyl hydrazides: a three-component reaction to construct fully substituted pyrazoles using TBAI/TBHP.

A mild and rapid approach has been developed for the construction of fully substituted pyrazoles using TBAI as a catalyst and TBHP as an oxidant, in which tosylhydrazide functions as the ring component and sulfonyl precursor. This protocol features a wide substrate scope with a broad range of functional group tolerance, utilizes easily available starting materials, can be scaled-up, and is operationally simple.

[1]  G. Hong,et al.  Tetrabutylammonium Iodide‐Catalyzed Radical Alkoxycarbonylation of 2‐Isocyanobiphenyls with Carbazates: Synthesis of Phenanthridine‐6‐carboxylates , 2014 .

[2]  Yi Pan,et al.  Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes. , 2014, Organic letters.

[3]  A. Lei,et al.  Revealing the metal-like behavior of iodine: an iodide-catalysed radical oxidative alkenylation. , 2014, Chemical communications.

[4]  Peng Du,et al.  Co-catalyzed synthesis of 1,4-dicarbonyl compounds using TBHP oxidant. , 2014, Organic letters.

[5]  C. Bolm,et al.  C-H activation of methyl arenes in the MnO2-mediated aroylation of N-chlorosulfoximines. , 2014, Organic letters.

[6]  Xiaoguang Bao,et al.  Nucleophilic attack of α-aminoalkyl radicals on carbon-nitrogen triple bonds to construct α-amino nitriles: an experimental and computational study. , 2013, Chemistry.

[7]  Wenteng Chen,et al.  One-pot three-component approach to the synthesis of polyfunctional pyrazoles. , 2013, Organic letters.

[8]  C. Frost,et al.  Ruthenium-catalyzed C-H functionalization of arylpyrazoles: regioselective acylation with acid chlorides. , 2013, Organic letters.

[9]  X. Wan,et al.  Iodide-catalyzed synthesis of N-nitrosamines via C-N cleavage of nitromethane. , 2013, The Journal of organic chemistry.

[10]  S. Batra,et al.  Synthesis of 3H-pyrazolo[3,4-c]isoquinolines and thieno[3,2-c]isoquinolines via cascade imination/intramolecular decarboxylative coupling. , 2013, Organic letters.

[11]  J. T. Njardarson,et al.  An In-Pharm-ative Educational Poster Anthology Highlighting the Therapeutic Agents That Chronicle Our Medicinal History , 2013 .

[12]  Xiaoqing Li,et al.  Iron halide-mediated regio- and stereoselective halosulfonylation of terminal alkynes with sulfonylhydrazides: synthesis of (E)-β-chloro and bromo vinylsulfones. , 2013, The Journal of organic chemistry.

[13]  C. Valdés,et al.  Regioselective one-step synthesis of pyrazoles from alkynes and N-tosylhydrazones: [3+2] dipolar cycloaddition/[1,5] sigmatropic rearrangement cascade. , 2013, Angewandte Chemie.

[14]  X. Wan,et al.  A new strategy for the construction of α-amino acid esters via decarboxylation. , 2013, Organic letters.

[15]  L. Ackermann,et al.  Expedient C-H amidations of heteroaryl arenes catalyzed by versatile ruthenium(II) catalysts. , 2013, Organic letters.

[16]  Xiaoqing Li,et al.  I2/TBHP-mediated reaction of sulfonylhydrazides with alkynes: synthesis of (E)-β-iodovinyl sulfones , 2013 .

[17]  A. Edmunds,et al.  A Robust Protocol for Pd(II)-catalyzed C-3 Arylation of (1H) Indazoles and Pyrazoles: Total Synthesis of Nigellidine Hydrobromide. , 2013, Chemical science.

[18]  H. Adams,et al.  Synthesis of 4-fluoromethylsydnones and their participation in alkyne cycloaddition reactions. , 2013, The Journal of organic chemistry.

[19]  Wei Liu,et al.  Synthesis of oxindoles by iron-catalyzed oxidative 1,2-alkylarylation of activated alkenes with an aryl C(sp2)-H bond and a C(sp3)-H bond adjacent to a heteroatom. , 2013, Angewandte Chemie.

[20]  S. Rout,et al.  Easy access to benzylic esters directly from alkyl benzenes under metal-free conditions. , 2013, Chemical communications.

[21]  Yucai Tang,et al.  Tetrabutylammonium iodide catalyzed allylic sulfonylation of Baylis-Hillman acetates with sulfonylhydrazides in water. , 2013, Organic & biomolecular chemistry.

[22]  Lei Wang,et al.  Direct access to acylated azobenzenes via Pd-catalyzed C-H functionalization and further transformation into an indazole backbone. , 2013, Organic letters.

[23]  M. Doyle,et al.  Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. The role of transition metal salt. , 2013, Journal of the American Chemical Society.

[24]  C. Barbas,et al.  Organocatalytic amidation and esterification of aldehydes with activating reagents by a cross-coupling strategy. , 2012, Angewandte Chemie.

[25]  C. Tseng,et al.  Tandem cyclization of α-cyano α-alkynyl aryl ketones induced by tert-butyl hydroperoxide and tetrabutylammonium iodide. , 2012, Organic letters.

[26]  Canhua Zhou,et al.  Tetrabutylammonium iodide catalyzed allylic sulfonylation of α-methyl styrene derivatives with sulfonylhydrazides. , 2012, Chemical communications.

[27]  R. Lesyk,et al.  Synthesis of new 4-thiazolidinone-, pyrazoline-, and isatin-based conjugates with promising antitumor activity. , 2012, Journal of medicinal chemistry.

[28]  Etsuko Tokunaga,et al.  Regioselective synthesis of pyrazole triflones based on triflyl alkyne cycloadditions. , 2012, Organic letters.

[29]  J. P. Harrity,et al.  Synthesis of ynone trifluoroborates toward functionalized pyrazoles. , 2012, Organic letters.

[30]  L. Qu,et al.  nBu4NI-catalyzed direct synthesis of α-ketoamides from aryl methyl ketones with dialkylformamides in water using TBHP as oxidant. , 2012, Chemical communications.

[31]  J. P. Harrity,et al.  A general and regioselective synthesis of 5-trifluoromethyl-pyrazoles. , 2012, Organic letters.

[32]  Huayou Hu,et al.  Tetrabutylammonium iodide catalyzed synthesis of allylic ester with tert-butyl hydroperoxide as an oxidant. , 2012, Organic letters.

[33]  Y. Janin.  Preparation and chemistry of 3/5-halogenopyrazoles. , 2012, Chemical reviews.

[34]  Bin Wang,et al.  nBu4NI-catalyzed C3-formylation of indoles with N-methylaniline. , 2012, Chemical communications.

[35]  Xuesen Fan,et al.  Synthesis of 3,5-disubstituted pyrazoles via cyclocondensation of 1,2-allenic ketones with hydrazines: application to the synthesis of 5-(5-methyl-pyrazol-3-yl)-2′-deoxycytidine , 2012 .

[36]  X. Wan,et al.  Cross coupling of acyl and aminyl radicals: direct synthesis of amides catalyzed by Bu4NI with TBHP as an oxidant. , 2012, Angewandte Chemie.

[37]  M. Klussmann,et al.  A comparative mechanistic study of Cu-catalyzed oxidative coupling reactions with N-phenyltetrahydroisoquinoline. , 2012, Journal of the American Chemical Society.

[38]  F. K. Keter,et al.  Perspective: the potential of pyrazole-based compounds in medicine , 2012, BioMetals.

[39]  Yixiang Cheng,et al.  Metal-free, organocatalytic cascade formation of C-N and C-O bonds through dual sp3 C-H activation: oxidative synthesis of oxazole derivatives. , 2012, Chemical communications.

[40]  S. Tkachenko,et al.  Synthesis and structure-activity relationship (SAR) of (5,7-disubstituted 3-phenylsulfonyl-pyrazolo[1,5-a]pyrimidin-2-yl)-methylamines as potent serotonin 5-HT(6) receptor (5-HT(6)R) antagonists. , 2011, Journal of medicinal chemistry.

[41]  X. Wan,et al.  Direct condensation of sulfonamide and formamide: NaI-catalyzed synthesis of N-sulfonyl formamidine using TBHP as oxidant. , 2011, Organic letters.

[42]  Wei Yu,et al.  TBAI-catalyzed oxidative coupling of aminopyridines with β-keto esters and 1,3-diones-synthesis of imidazo[1,2-a]pyridines. , 2011, Chemical communications.

[43]  X. Wan,et al.  Synthesis of tert-butyl peresters from aldehydes by Bu4NI-catalyzed metal-free oxidation and its combination with the Kharasch-Sosnovsky reaction. , 2011, Chemical communications.

[44]  María Sánchez-Roselló,et al.  From 2000 to mid-2010: a fruitful decade for the synthesis of pyrazoles. , 2011, Chemical reviews.

[45]  A. Schmidt,et al.  Recent Advances in the Chemistry of Pyrazoles. Part 2. Reactions and N-Heterocyclic Carbenes of Pyrazole , 2011 .

[46]  Yongfang Li,et al.  Sulfonyl: a new application of electron-withdrawing substituent in highly efficient photovoltaic polymer. , 2011, Chemical communications.

[47]  Jianqiang Qian,et al.  A novel synthesis of fluorinated pyrazoles via gold(I)-catalyzed tandem aminofluorination of alkynes in the presence of Selectfluor. , 2011, Organic letters.

[48]  Metin Zora,et al.  Synthesis of pyrazoles via electrophilic cyclization. , 2011, The Journal of organic chemistry.

[49]  B. Nachtsheim,et al.  A metal-free amination of benzoxazoles--the first example of an iodide-catalyzed oxidative amination of heteroarenes. , 2011, Organic letters.

[50]  K. Ishihara,et al.  In situ generated (hypo)iodite catalysts for the direct α-oxyacylation of carbonyl compounds with carboxylic acids. , 2011, Angewandte Chemie.

[51]  T. Taniguchi,et al.  Iron-catalyzed sulfonyl radical formations from sulfonylhydrazides and oxidative addition to alkenes. , 2011, Organic & biomolecular chemistry.

[52]  X. Wan,et al.  Bu4NI-catalyzed C-O bond formation by using a cross-dehydrogenative coupling (CDC) reaction. , 2011, Chemistry.

[53]  Benjamin Willy,et al.  Rapid one-pot, four-step synthesis of highly fluorescent 1,3,4,5-tetrasubstituted pyrazoles. , 2011, Organic letters.

[54]  T. Taniguchi,et al.  Iron-catalyzed oxidative addition of alkoxycarbonyl radicals to alkenes with carbazates and air. , 2010, Angewandte Chemie.

[55]  F. Glorius,et al.  Efficient synthesis of pyrazoles: oxidative C-C/N-N bond-formation cascade. , 2010, Angewandte Chemie.

[56]  J. M. Mínguez,et al.  Regioselective palladium-catalyzed arylation of 4-chloropyrazoles. , 2010, Organic letters.

[57]  Nicholas A. McGrath,et al.  A Graphical Journey of Innovative Organic Architectures That Have Improved Our Lives , 2010 .

[58]  N. de Kimpe,et al.  New synthesis of fluorinated pyrazoles. , 2010, Organic letters.

[59]  S. Tanase,et al.  Coordination Versatility of Pyrazole‐Based Ligands towards High‐Nuclearity Transition‐Metal and Rare‐Earth Clusters , 2010 .

[60]  Takashi Okitsu,et al.  Reagent-controlled oxidative aromatization in iodocyclization: switchable access to dihydropyrazoles and pyrazoles. , 2010, Organic letters.

[61]  S. Tkachenko,et al.  (3-Phenylsulfonylcycloalkano[e and d]pyrazolo[1,5-a]pyrimidin-2-yl)amines: potent and selective antagonists of the serotonin 5-HT6 receptor. , 2010, Journal of medicinal chemistry.

[62]  Huanrong Li,et al.  Iron-catalyzed N-alkylation of azoles via oxidation of C-H bond adjacent to an oxygen atom. , 2010, Organic letters.

[63]  S. Fustero,et al.  Recent Advances in the Synthesis of Pyrazoles. A Review , 2009 .

[64]  D. Browne,et al.  Investigation of the scope and regiochemistry of alkynylboronate cycloadditions with sydnones. , 2009, Journal of the American Chemical Society.

[65]  Jeremy T Starr,et al.  One-pot synthesis of N-arylpyrazoles from arylhalides. , 2009, Organic letters.

[66]  M. Halcrow.  Pyrazoles and pyrazolides-flexible synthons in self-assembly. , 2009, Dalton transactions.

[67]  D. Sames,et al.  C-H bonds as ubiquitous functionality: a general approach to complex arylated pyrazoles via sequential regioselective C-arylation and N-alkylation enabled by SEM-group transposition. , 2009, Journal of the American Chemical Society.

[68]  D. Browne,et al.  Cross coupling of bromo sydnones: development of a flexible route toward functionalized pyrazoles. , 2009, The Journal of organic chemistry.

[69]  I. Davies,et al.  A simple, modular method for the synthesis of 3,4,5-trisubstituted pyrazoles. , 2008, The Journal of organic chemistry.

[70]  Xiaohu Deng,et al.  Regioselective synthesis of 1,3,5-tri- and 1,3,4,5-tetrasubstituted pyrazoles from N-arylhydrazones and nitroolefins. , 2008, The Journal of organic chemistry.

[71]  D. Browne,et al.  A sydnone cycloaddition route to pyrazole boronic esters. , 2007, Angewandte Chemie.

[72]  S. Rault,et al.  A facile synthetic route to new pyrazoloisoindolones , 2007 .

[73]  J. Ready,et al.  Copper-promoted cycloaddition of diazocarbonyl compounds and acetylides. , 2007, Angewandte Chemie.

[74]  A. Fossa,et al.  Zoniporide: a potent and selective inhibitor of the human sodium-hydrogen exchanger isoform 1 (NHE-1). , 2006, Cardiovascular drug reviews.

[75]  S. Natarajan,et al.  1,3-diketones from acid chlorides and ketones: a rapid and general one-pot synthesis of pyrazoles. , 2006, Organic letters.

[76]  Youhong Hu,et al.  Three-component, one-pot reaction for the combinatorial synthesis of 1,3,4-substituted pyrazoles. , 2006, Journal of combinatorial chemistry.

[77]  T. Norris,et al.  New hydroxy-pyrazoline intermediates, subtle regio-selectivity and relative reaction rate variations observed during acid catalyzed and neutral pyrazole cyclization. , 2005, Organic & biomolecular chemistry.

[78]  E. Torrente,et al.  Efficient synthesis of enantiomerically pure alpha-alkyl cyclopropanecarbonitrile derivatives from pyrazolines. , 2004, Organic letters.

[79]  Chao‐Jun Li,et al.  CuBr-catalyzed efficient alkynylation of sp3 C-H bonds adjacent to a nitrogen atom. , 2004, Journal of the American Chemical Society.

[80]  C. Liao,et al.  Regulation of cell growth by selective COX-2 inhibitors in oral carcinoma cell lines. , 2003, Prostaglandins & other lipid mediators.

[81]  Jae Nyoung Kim,et al.  Regioselective synthesis of 1,3,4,5-tetrasubstituted pyrazoles from Baylis–Hillman adducts , 2003 .

[82]  S. Swaney,et al.  Novel 1,5-diphenylpyrazole nonnucleoside HIV-1 reverse transcriptase inhibitors with enhanced activity versus the delavirdine-resistant P236L mutant: lead identification and SAR of 3- and 4-substituted derivatives. , 2000, Journal of medicinal chemistry.

[83]  Y. Kurasawa,et al.  Synthesis of pyrazoles , 1998 .

[84]  Andrew Simon Bell,et al.  Sildenafil (VIAGRATM), a potent and selective inhibitor of type 5 cGMP phosphodiesterase with utility for the treatment of male erectile dysfunction , 1996 .

[85]  Eric J. Kantorowski,et al.  Bis(sulfonyl) Ketones: A New Oxyallyl Cation Source , 1995 .

[86]  S. Trofimenko.  Recent advances in poly(pyrazolyl)borate (scorpionate) chemistry , 1993 .

[87]  David J. Williams,et al.  New sulfonyl-containing materials for nonlinear optics: semiempirical calculations, synthesis, and properties , 1990 .

[88]  M. Wilson,et al.  Inhibitors of cholesterol biosynthesis. 2. 1,3,5-trisubstituted [2-(tetrahydro-4-hydroxy-2-oxopyran-6-yl)ethyl]pyrazoles. , 1990, Journal of medicinal chemistry.