Metal-Free Cross-Dehydrogenative Coupling (CDC): Molecular Iodine as a Versatile Catalyst/Reagent for CDC Reactions.

The development of ecofriendly methods for carbon-carbon (C-C) and carbon-heteroatom (C-Het) bond formation is of great significance in modern-day research. Metal-free cross-dehydrogenative coupling (CDC) has emerged as an important tool for organic and medicinal chemists as a means to form C-C and C-Het bonds, as it is atom economical and more efficient and greener than transition-metal catalyzed CDC reactions. Molecular iodine (I2 ) is recognized as an inexpensive, environmentally benign, and easy-to-handle catalyst or reagent to pursue CDCs under mild reaction conditions, with good regioselectivities and broad substrate compatibility. This review presents the recent developments of I2 -catalyzed C-C, C-N, C-O, and C-S/C-Se bond-forming reactions for the synthesis of various important organic molecules by cross-dehydrogenative coupling.

[1]  G. J. Chuang,et al.  (Diacetoxyiodo)benzene-Mediated C–H Oxidation of Benzylic Acetals , 2019, ACS omega.

[2]  H. Behbehani,et al.  Synthetic Strategy for Pyrazolo[1,5-a]pyridine and Pyrido[1,2-b]indazole Derivatives through AcOH and O2-Promoted Cross-dehydrogenative Coupling Reactions between 1,3-Dicarbonyl Compounds and N-Amino-2-iminopyridines , 2019, ACS omega.

[3]  H. Behbehani,et al.  Sustainable Synthetic Approach for (Pyrazol-4-ylidene)pyridines By Metal Catalyst-Free Aerobic C(sp2)–C(sp3) Coupling Reactions between 1-Amino-2-imino-pyridines and 1-Aryl-5-pyrazolones , 2019, ACS omega.

[4]  S. Mukherjee,et al.  Microwave-assisted Iodine-catalyzed Rapid Synthesis of 6H-indolo[2,3-b] quinolines: Formal Synthesis of Cryptotackieine , 2017 .

[5]  M. Shi,et al.  Synthesis of Cyclic and Heterocyclic Compounds via Gold-Catalyzed Reactions , 2017, Synlett.

[6]  K. R. Prabhu,et al.  Iodine-catalyzed sulfenylation of pyrazolones using dimethyl sulfoxide as an oxidant. , 2017, Organic & biomolecular chemistry.

[7]  R. Peddinti,et al.  Iodine-catalysed regioselective synthesis of β-hydroxysulfides , 2017 .

[8]  K. Sun,et al.  A novel metal-free method for the selenocyanation of aromatic ketones to afford α-carbonyl selenocyanates. , 2017, Organic & biomolecular chemistry.

[9]  J. Qu,et al.  Molecular Iodine-Mediated α-C-H Oxidation of Pyrrolidines to N,O-Acetals: Synthesis of (±)-Preussin by Late-Stage 2,5-Difunctionalizations of Pyrrolidine. , 2017, The Journal of organic chemistry.

[10]  Hongwei Zhang,et al.  Selective Piperidine Synthesis Exploiting Iodine-Catalyzed Csp3–H Amination under Visible Light , 2017 .

[11]  S. Yin,et al.  Intramolecular, Site-Selective, Iodine-Mediated, Amination of Unactivated (sp3)C-H Bonds for the Synthesis of Indoline Derivatives. , 2017, Organic letters.

[12]  Ping Wu,et al.  I2/TBPB mediated oxidative reaction of aryl acetaldehydes with amidines: synthesis of 1,2,5-triaryl-1H-imidazoles , 2017 .

[13]  A. Gupta,et al.  Iodine-Catalyzed C-N Bond Formation: Synthesis of 3-Aminoquinoxalinones under Ambient Conditions. , 2017, The Journal of organic chemistry.

[14]  Hailing Liu,et al.  I2/TBHP-mediated oxidative coupling of ketones and toluene derivatives: a facile method for the preparation of α-benzoyloxy ketones , 2017 .

[15]  A. Itoh,et al.  Photo-oxidative Cross-Dehydrogenative Coupling-Type Reaction of Thiophenes with α-Position of Carbonyls Using a Catalytic Amount of Molecular Iodine. , 2017, Organic letters.

[16]  Kang-ping Xu,et al.  Iodine-Mediated One-Pot Synthesis of 2-(Piperazin-1-yl)pyrazine Derivatives from N-Alkyl Piperazines , 2017 .

[17]  Yangjie Wu,et al.  Iodine-Catalyzed Direct C-H Alkenylation of Azaheterocycle N-Oxides with Alkenes. , 2017, Organic letters.

[18]  Mohit L. Deb,et al.  Iodine/Hydrogen Peroxide Promoted Intramolecular Oxidative C–O Bond Formation in Ethanol at Room Temperature: A Green Approach to 1,3-Oxazines , 2016 .

[19]  Pengfei Sun,et al.  Metal-free iodine-catalyzed direct cross-dehydrogenative coupling (CDC) between pyrazoles and thiols , 2016 .

[20]  Paramjit Singh,et al.  Cross Dehydrogenative Coupling (CDC) Reactions of N,N-Disubstituted Formamides, Benzaldehydes and Cycloalkanes , 2016 .

[21]  Jeh-Jeng Wang,et al.  Iodine-promoted cyclization of N-propynyl amides and N-allyl amides via sulfonylation and sulfenylation. , 2016, Chemical communications.

[22]  W. Deng,et al.  Regioselective Iodine-Catalyzed Construction of Polysubstituted Pyrroles from Allenes and Enamines. , 2016, The Journal of organic chemistry.

[23]  K. R. Prabhu,et al.  Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles Using Dimethyl Sulfoxide as an Oxidant. , 2016, The Journal of organic chemistry.

[24]  A. Verma,et al.  Iodine-mediated synthesis of heterocycles via electrophilic cyclization of alkynes. , 2016, Organic & biomolecular chemistry.

[25]  Ramachandra Reddy Donthiri,et al.  Iodine-catalyzed [3+2] cyclization of 2-pyridylesters and chalcones: metal-free approach for the synthesis of substituted indolizines , 2016 .

[26]  Hua Wang,et al.  Iodine-catalyzed Direct Thiolation of Indoles with Thiols Leading to 3-Thioindoles Using Air as the Oxidant , 2016, Catalysis Letters.

[27]  Leiyang Lv,et al.  Fe-Catalyzed Cross-Dehydrogenative Coupling Reactions , 2016, Topics in Current Chemistry.

[28]  Haojie Ma,et al.  Iodine‐Catalyzed Regioselective Sulfenylation of Indoles with Thiols in Water , 2016 .

[29]  Xiao‐Qi Yu,et al.  Iodine-mediated synthesis of 3-acylbenzothiadiazine 1,1-dioxides , 2016, Beilstein journal of organic chemistry.

[30]  Yan‐Dong Wu,et al.  Iodine-Promoted Oxidative Cross-Coupling of Unprotected Anilines with Methyl Ketones: A Site-Selective Direct C-H Bond Functionalization to C4-Dicarbonylation of Anilines. , 2016, Organic letters.

[31]  Luo Yang,et al.  Iodine-Catalyzed Oxidative Functionalization of Azaarenes with Benzylic C(sp(3))-H Bonds via N-Alkylation/Amidation Cascade: Two-Step Synthesis of Isoindolo[2,1-b]isoquinolin-7(5H)-one. , 2016, Organic letters.

[32]  Xinquan Hu,et al.  Metal-free, iodine-catalyzed regioselective sulfenylation of indoles with thiols , 2016 .

[33]  P. Retailleau,et al.  Molecular Iodine-Catalyzed Aerobic α,β-Diamination of Cyclohexanones with 2-Aminopyrimidine and 2-Aminopyridines. , 2016, Organic letters.

[34]  Li-Xia Wang,et al.  Iodine‐Catalyzed Oxidative Benzylic C−H Bond Amination of Azaarenes: Practical Synthesis of Quinazolin‐4(3 H)‐ones , 2016 .

[35]  Maozhong Miao,et al.  I2-Catalyzed Oxidative Coupling Reactions of Hydrazones and Amines and the Application in the Synthesis of 1,3,5-Trisubstituted 1,2,4-Triazoles. , 2016, Organic letters.

[36]  S. Tilve,et al.  Iodine-Mediated Intramolecular Dehydrogenative Coupling: Synthesis of N-Alkylindolo[3,2-c]- and -[2,3-c]quinoline Iodides. , 2016, Organic letters.

[37]  Nandkishor N. Karade,et al.  Metal-free new synthesis of 1,3-naphthoxazines via intramolecular cross dehydrogenative-coupling reaction of 1-(α-aminoalkyl)-2-naphthols using hypervalent iodine(III) reagent , 2016 .

[38]  N. Tada,et al.  Intermolecular Cyclopropanation of Styrenes Using Iodine and Visible Light via Carbon-Iodine Bond Cleavage. , 2016, Organic letters.

[39]  A. Wu,et al.  Molecular iodine mediated oxidative cross-coupling of sp3 C–H with sp2 C–H: direct synthesis of substituted indolo[2,3-b]carbazoles via formal [2+2+1+1] cyclization , 2015 .

[40]  E. Martín,et al.  Hypervalent Activation as a Key Step for Dehydrogenative ortho C-C Coupling of Iodoarenes. , 2015, Chemistry.

[41]  Baomin Wang,et al.  Iodine-catalysed versatile sulfenylation of indoles with thiophenols: controllable synthesis of mono- and bis-arylthioindoles , 2015 .

[42]  E. Kwon,et al.  Oxidative Amidation of Nitroalkanes with Amine Nucleophiles using Molecular Oxygen and Iodine. , 2015, Angewandte Chemie.

[43]  A. Antonchick,et al.  Hypervalent Iodine(III) in Direct Carbon-Hydrogen Bond Functionalization , 2015 .

[44]  Pengfei Sun,et al.  Direct thiolation of methoxybenzenes with thiols under metal-free conditions by iodine catalysis , 2015 .

[45]  Dong Wang,et al.  Iodine-Catalyzed Direct Olefination of 2-Oxindoles and Alkenes via Cross-Dehydrogenative Coupling (CDC) in Air. , 2015, Organic letters.

[46]  Chen Yu,et al.  A Convenient Catalytic Procedure for Direct Synthesis of Aryl­selanyl Anilines , 2015 .

[47]  Jian-rong Gao,et al.  Iodine-Promoted Construction of Polysubstituted 2,3-Dihydropyrroles from Chalcones and β-Enamine Ketones (Esters). , 2015, Organic letters.

[48]  Laijin Tian,et al.  Facile Access to Benzothiophenes through Metal-Free Iodine-­Catalyzed Intermolecular Cyclization of Thiophenols and Alkynes , 2015 .

[49]  R. Peddinti,et al.  Iodine catalyzed cross-dehydrogenative C–S coupling by C(sp2)–H bond activation: direct access to aryl sulfides from aryl thiols , 2015 .

[50]  Hua Wang,et al.  Metal-Free Iodine-Catalyzed Direct Arylthiation of Substituted Anilines with Thiols. , 2015, The Journal of organic chemistry.

[51]  R. Vishwakarma,et al.  Iodine-DMSO promoted C–H (SP3) functionalization approach to α-ketoamides , 2015 .

[52]  A. Chaskar,et al.  Iodine-Mediated Domino Protocol for the Synthesis of Benz­amides from Ethylarenes via sp3 C–H Functionalization , 2015 .

[53]  Y. Lan,et al.  Tuning radical reactivity using iodine in oxidative C(sp(3))-H/C(sp)-H cross-coupling: an easy way toward the synthesis of furans and indolizines. , 2015, Chemical communications.

[54]  Xinquan Hu,et al.  Iodine-catalyzed C–H/S–H oxidative coupling: from 1,3-diketones and thiophenols to β-dicarbonyl thioethers , 2015 .

[55]  M. Gao,et al.  Iodine-catalyzed radical oxidative annulation for the construction of dihydrofurans and indolizines. , 2015, Organic letters.

[56]  G. Satish,et al.  Iodine-Mediated C-H Functionalization of sp, sp(2), and sp(3) Carbon: A Unified Multisubstrate Domino Approach for Isatin Synthesis. , 2015, The Journal of organic chemistry.

[57]  Dong Liu,et al.  Iodine-catalyzed oxidative coupling reactions utilizing C - H and X - H as nucleophiles. , 2015, Chemistry, an Asian journal.

[58]  B. A. Shah,et al.  C-H functionalization of terminal alkynes towards stereospecific synthesis of (E) or (Z) 2-methylthio-1,4-ene-diones. , 2015, Chemical communications.

[59]  Yan Jiang,et al.  Iodine-catalyzed ammoxidation of methyl arenes. , 2015, Chemical communications.

[60]  S. Berteina‐Raboin,et al.  Iodine-catalyzed regioselective sulfenylation of imidazoheterocycles in PEG400 , 2015 .

[61]  Meenakshi,et al.  Transition metal free intramolecular selective oxidative C(sp3)-N coupling: synthesis of N-aryl-isoindolinones from 2-alkylbenzamides. , 2015, Chemical communications.

[62]  T. Miura,et al.  Metal-free synthesis of imidazopyridine from nitroalkene and 2-aminopyridine in the presence of a catalytic amount of iodine and aqueous hydrogen peroxide , 2015 .

[63]  S. Skoulika,et al.  Iodine-Mediated Diastereoselective Cyclopropanation of Arylidene Malononotriles by 2,6-Dimethylquinoline , 2015, Synlett.

[64]  A. Chaskar,et al.  I2 catalyzed tandem protocol for synthesis of quinoxalines via sp3, sp2 and sp C–H functionalization , 2015 .

[65]  A. Lei,et al.  I₂-catalyzed oxidative C(sp³)-H/S-H coupling: utilizing alkanes and mercaptans as the nucleophiles. , 2014, Chemical communications.

[66]  A. Wu,et al.  Iodine‐Promoted Sequential C(sp3) ? H Functionalization Reactions: An Annulation Strategy for the Construction of 3‐Methylthio‐4‐arylmaleimides , 2014 .

[67]  Xiaoqiang Zhou,et al.  I2-mediated oxidative cyclization for synthesis of substituted indolizines. , 2014, The Journal of organic chemistry.

[68]  G. Sekar,et al.  An efficient route to synthesize isatins by metal-free, iodine-catalyzed sequential C(sp(3))-H oxidation and intramolecular C-N bond formation of 2'-aminoacetophenones. , 2014, Organic & biomolecular chemistry.

[69]  Wenlong Wei,et al.  Iodine-catalysed sp3 C–H sulfonylation to form β-dicarbonyl sulfones with sodium sulfinates , 2014 .

[70]  Kai-lu Zheng,et al.  Iodine-promoted efficient synthesis of diheteroaryl thioethers via the integration of iodination/condensation/cyclization/dehydration sequences , 2014 .

[71]  B. A. Shah,et al.  A general metal free approach to α-ketoamides via oxidative amidation-diketonization of terminal alkynes. , 2014, Chemical communications.

[72]  Gunaganti Naresh,et al.  Molecular iodine mediated synthesis of polysubstituted oxazoles by oxidative domino cyclization in water , 2014 .

[73]  Thomas Knauber,et al.  Dehydrierende Kreuzkupplungen von C sp 3‐H‐Bindungen: vielseitige Verfahren zur Bildung von C‐C‐Bindungen , 2014 .

[74]  Chao‐Jun Li,et al.  The cross-dehydrogenative coupling of C(sp3)-H bonds: a versatile strategy for C-C bond formations. , 2014, Angewandte Chemie.

[75]  S. Rout,et al.  Iodine-catalysed oxidative cyclisation of acylhydrazones to 2,5-substituted 1,3,4-oxadiazoles , 2014 .

[76]  Yunfeng Liao,et al.  Iodine-catalyzed efficient 2-arylsulfanylphenol formation from thiols and cyclohexanones , 2013 .

[77]  T. Miura,et al.  Molecular-iodine-catalyzed aerobic photooxidative C–C bond formation between tertiary amines and carbon nucleophiles , 2013 .

[78]  Huanfeng Jiang,et al.  Metal-free synthesis of 2-aminobenzothiazoles via aerobic oxidative cyclization/dehydrogenation of cyclohexanones and thioureas. , 2013, Organic letters.

[79]  Renchun Yang,et al.  Molecular iodine-catalyzed multicomponent reactions: an efficient catalyst for organic synthesis , 2013 .

[80]  H. Togo,et al.  Iodine-Mediated α-Sulfonyloxylation of Alkyl Aryl Ketones with Oxone® and Sulfonic Acids , 2013 .

[81]  K. R. Prabhu,et al.  A versatile C-H functionalization of tetrahydroisoquinolines catalyzed by iodine at aerobic conditions. , 2013, Organic letters.

[82]  T. Miura,et al.  Molecular iodine catalyzed cross-dehydrogenative coupling reaction between two sp3 C-H bonds using hydrogen peroxide. , 2013, Organic letters.

[83]  Huanfeng Jiang,et al.  Practical Synthesis of Polysubstituted Imidazoles via Iodine‐ Catalyzed Aerobic Oxidative Cyclization of Aryl Ketones and Benzylamines , 2013 .

[84]  A. Wu,et al.  Metal-free dual sp3 C–H functionalization: I2-promoted domino oxidative cyclization to construct 2,5-disubstituted oxazoles , 2013 .

[85]  B. Banik,et al.  Stereospecific novel glycosylation of hydroxy β-lactams via iodine-catalyzed reaction: a new method for optical resolution , 2012 .

[86]  Y. R. Lee,et al.  Iodine-catalyzed efficient synthesis of azaarene substituted 3-hydroxy-2-oxindole derivatives through sp3 C–H functionalization , 2012 .

[87]  B. Banik,et al.  An E xpeditious Iodine-Catalyzed Synthesis of 3-Pyrrole-substituted 2-Azetidinones , 2012, Molecules.

[88]  Baohua Chen,et al.  Iodine-induced regioselective direct alkylation of azoles via in situ formed alkyliodide , 2012 .

[89]  Zhiyong Wang,et al.  Selective iodine-catalyzed intermolecular oxidative amination of C(sp3)-H bonds with ortho-carbonyl-substituted anilines to give quinazolines. , 2012, Angewandte Chemie.

[90]  Lei Wang,et al.  TBHP/I2-promoted oxidative coupling of acetophenones with amines at room temperature under metal-free and solvent-free conditions for the synthesis of α-ketoamides , 2012 .

[91]  R. Pawar,et al.  Molecular Iodine: An Efficient and Versatile Reagent for Organic Synthesis , 2012 .

[92]  P. Parvatkar,et al.  Recent developments in the synthesis of five- and six-membered heterocycles using molecular iodine. , 2012, Chemistry.

[93]  M. Bhat,et al.  Iodine catalyzed one-pot synthesis of chloro-substituted linear and angular indoloquinolines and in vitro antiproliferative activity study of different indoloquinolines , 2012, Medicinal Chemistry Research.

[94]  Xi‐Cun Wang,et al.  Molecular Iodine Promoted Synthesis of New Pyrido[2,3‐d]pyrimidin‐4‐ols , 2011 .

[95]  Zhiping Li,et al.  I2-catalyzed indole formation via oxidative cyclization of N-aryl enamines. , 2011, Chemistry, an Asian journal.

[96]  Huanfeng Jiang,et al.  TBHP/I2-mediated domino oxidative cyclization for one-pot synthesis of polysubstituted oxazoles. , 2010, Organic letters.

[97]  K. Nicholas,et al.  Iodine-catalyzed aminosulfonation of hydrocarbons by imidoiodinanes. A synthetic and mechanistic investigation. , 2010, The Journal of organic chemistry.

[98]  S. Mukherjee,et al.  An Effective Microwave-Induced Iodine-Catalyzed Method for the Synthesis of Quinoxalines via Condensation of 1,2-Diamines with 1,2-Dicarbonyl Compounds , 2010, Molecules.

[99]  Zhiyong Wang,et al.  A simple and efficient approach to the synthesis of 2-phenylquinazolines via sp(3) C-H functionalization. , 2010, Organic letters.

[100]  S. Mukherjee,et al.  An Expeditious Synthesis of N-substituted Pyrroles via Microwave-Induced Iodine-Catalyzed Reactions under Solventless Conditions , 2010, Molecules.

[101]  Caroline J. Scheuermann Beyond traditional cross couplings: the scope of the cross dehydrogenative coupling reaction. , 2010, Chemistry, an Asian journal.

[102]  B. Banik,et al.  A FACILE IODINE-CATALYZED GLYCOSYLATION: ENANTIOMERICALLY PURE β-LACTAMS WITH THE THIENAMYCIN SIDE CHAIN , 2009 .

[103]  P. Parvatkar,et al.  An expeditious I2-catalyzed entry into 6H-indolo[2,3-b]quinoline system of cryptotackieine. , 2009, The Journal of organic chemistry.

[104]  Chao‐Jun Li Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations. , 2009, Accounts of chemical research.

[105]  H. Togo,et al.  Synthetic Use of Molecular Iodine for Organic Synthesis , 2006 .

[106]  Chao‐Jun Li,et al.  Cu-catalyzed cross-dehydrogenative coupling: a versatile strategy for C-C bond formations via the oxidative activation of sp(3) C-H bonds. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[107]  Chao‐Jun Li,et al.  Green chemistry: The development of cross-dehydrogenative coupling (CDC) for chemical synthesis , 2006 .

[108]  B. Banik,et al.  Iodine-catalyzed highly efficient Michael reaction of indoles under solvent-free condition , 2005 .

[109]  B. Banik,et al.  A remarkable iodine-catalyzed protection of carbonyl compounds , 2005 .

[110]  B. Banik,et al.  Simple synthesis of substituted pyrroles. , 2004, The Journal of organic chemistry.

[111]  M. K. Basu,et al.  A New Molecular Iodine-Catalyzed Acetalization of Carbonyl Compounds , 2002 .

[112]  M. K. Basu,et al.  A new molecular iodine-catalyzed thioketalization of carbonyl compounds: selectivity and scope , 2001 .

[113]  Louis Rosenfeld,et al.  Discovery and Early Uses of Iodine , 2000 .