Copper-Mediated Thiolation of Unactivated Heteroaryl C-H Bonds with Disulfides under Ligand- and Metal-Oxidant-Free Conditions

Various sulfenylated heteroarenes were synthesized by a copper-mediated C−H thiolation, which was assisted by a 2-(pyridin-2-yl)isopropylamine (PIP-amine) directing group. The reaction features a broad substrate scope, good functional group tolerance, ligand- and metal-oxidant-free conditions, exceptional compatibility with aliphatic disulfides, and excellent yields, providing a highly efficient approach to the biologically important sulfenylated heteroarenes.

[1]  L. Ackermann,et al.  Photo-induced copper-catalyzed C-H chalcogenation of azoles at room temperature. , 2017, Chemical communications.

[2]  jin-quan yu,et al.  Copper-Mediated Late-Stage Functionalization of Heterocycle-Containing Molecules. , 2017, Angewandte Chemie.

[3]  L. Ackermann,et al.  Expedient C–H Chalcogenation of Indolines and Indoles by Positional-Selective Copper Catalysis , 2017 .

[4]  Y. Nishihara,et al.  Palladium-catalysed direct thiolation and selenation of aryl C-H bonds assisted by directing groups. , 2016, Dalton transactions.

[5]  Hongli Wang,et al.  Recent Progress on Copper-Mediated Directing-Group-Assisted C(sp2)–H Activation , 2016, Synthesis.

[6]  L. Ackermann,et al.  Overcoming the Limitations of C-H Activation with Strongly Coordinating N-Heterocycles by Cobalt Catalysis. , 2016, Angewandte Chemie.

[7]  Bing‐Feng Shi,et al.  Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds , 2016 .

[8]  L. Ackermann,et al.  Weak O-Assistance Outcompeting Strong N,N-Bidentate Directing Groups in Copper-Catalyzed C-H Chalcogenation. , 2016, Chemistry.

[9]  J. Li,et al.  2-Aminophenyl-1H-pyrazole as a Removable Directing Group for Copper-Mediated C-H Amidation and Sulfonamidation. , 2016, Organic letters.

[10]  Jidan Liu,et al.  Copper-Catalyzed or -Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups , 2016 .

[11]  G. He,et al.  Syntheses and Transformations of α-Amino Acids via Palladium-Catalyzed Auxiliary-Directed sp(3) C-H Functionalization. , 2016, Accounts of chemical research.

[12]  O. Daugulis,et al.  A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp(2) C-H Bond Amination. , 2016, Journal of the American Chemical Society.

[13]  Jidan Liu,et al.  Copper-Mediated ortho-Arylation of Benzamides with Arylboronic Acid , 2016 .

[14]  T. Punniyamurthy,et al.  Copper(II)-mediated regioselective N-arylation of pyrroles, indoles, pyrazoles and carbazole via dehydrogenative coupling. , 2016, Chemical communications.

[15]  Raja K. Rit,et al.  Reusable and Removable Directing Groups for C(sp2)−H Bond Functionalization of Arenes , 2015 .

[16]  J. You,et al.  Copper-Catalyzed Intramolecular Dehydrogenative Amidation of Unactivated C(sp(3))-H Bonds Using O2 as the Sole Oxidant. , 2015, The Journal of organic chemistry.

[17]  Jun Yuan,et al.  Copper-catalyzed oxidative C-H/C-H cross-coupling of benzamides and thiophenes. , 2015, Chemical communications.

[18]  Bing‐Feng Shi,et al.  Copper-/Silver-Mediated Arylation of C(sp(2))-H Bonds with 2-Thiophenecarboxylic Acids. , 2015, Organic letters.

[19]  Bing‐Feng Shi,et al.  Copper(II)-Catalyzed Direct Sulfonylation of C(sp(2))-H Bonds with Sodium Sulfinates. , 2015, Organic letters.

[20]  S. Yin,et al.  Copper-mediated thiolation of carbazole derivatives and related N-heterocycle compounds , 2015 .

[21]  Xiaodong Shi,et al.  Nickel-catalyzed directed sulfenylation of sp(2) and sp(3) C-H bonds. , 2015, Chemical communications.

[22]  B. Liu,et al.  Nickel-catalyzed direct thiolation of unactivated C(sp(3))-H bonds with disulfides. , 2015, Chemical communications.

[23]  S. Yin,et al.  Nickel-catalyzed direct thiolation of C(sp(3))-H bonds in aliphatic amides. , 2015, Organic letters.

[24]  Jidan Liu,et al.  Copper-mediated ortho C-H sulfonylation of benzoic acid derivatives with sodium sulfinates. , 2015, Chemical communications.

[25]  Bing‐Feng Shi,et al.  Copper-catalyzed direct acyloxylation of C(sp2)-H bonds with Benzoic acids , 2015, Science China Chemistry.

[26]  N. Jiao,et al.  Cu- or Fe-catalyzed C–H/C–C bond nitrogenation reactions for the direct synthesis of N-containing compounds , 2015 .

[27]  L. Tran,et al.  Bidentate, monoanionic auxiliary-directed functionalization of carbon-hydrogen bonds. , 2015, Accounts of chemical research.

[28]  B. Liu,et al.  Copper-catalyzed ortho-halogenation of arenes and heteroarenes directed by a removable auxiliary. , 2015, Chemical communications.

[29]  Yuhong Zhang,et al.  Nickel-catalyzed direct thioetherification of β-C(sp(3))-H bonds of aliphatic amides. , 2015, Organic letters.

[30]  Yuhong Zhang,et al.  Direct ortho-thiolation of arenes and alkenes by nickel catalysis. , 2015, Organic letters.

[31]  Bing‐Feng Shi,et al.  Nickel-catalyzed thiolation of unactivated aryl C-H bonds: efficient access to diverse aryl sulfides. , 2015, Chemical communications.

[32]  A. Kadi,et al.  Nickel-catalyzed and benzoic acid-promoted direct sulfenylation of unactivated arenes. , 2015, Chemical communications.

[33]  Zhengxing Wu,et al.  Copper-catalyzed C-H functionalization reactions: efficient synthesis of heterocycles. , 2015, Chemical reviews.

[34]  Jun Yuan,et al.  Copper(II)-catalyzed methoxylation of unactivated (hetero)aryl C–H bonds using a removable bidentate auxiliary , 2015 .

[35]  Qiang Sun,et al.  Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation. , 2015, Chemical Society reviews.

[36]  Bing‐Feng Shi,et al.  Copper/silver-mediated direct ortho-ethynylation of unactivated (hetero)aryl C-H bonds with terminal alkyne. , 2015, Chemistry.

[37]  Jun-Fang Gong,et al.  Copper-mediated direct alkoxylation of arenes using an N,O-bidentate directing system. , 2014, The Journal of organic chemistry.

[38]  Bing‐Feng Shi,et al.  Cu(II)-mediated C-S/N-S bond formation via C-H activation: access to benzoisothiazolones using elemental sulfur. , 2014, Organic letters.

[39]  jin-quan yu,et al.  Bypassing the Limitations of Directed C–H Functionalizations of Heterocycles , 2014, Nature.

[40]  jin-quan yu,et al.  Exceedingly fast copper(II)-promoted ortho C-H trifluoromethylation of arenes using TMSCF₃. , 2014, Angewandte Chemie.

[41]  M. Kanai,et al.  Copper-mediated direct C(sp3)-H and C(sp2)-H acetoxylation. , 2014, Organic letters.

[42]  jin-quan yu,et al.  Cu(II)-mediated ortho C-H alkynylation of (hetero)arenes with terminal alkynes. , 2014, Journal of the American Chemical Society.

[43]  Bo Li,et al.  Copper-mediated hydroxylation of arenes and heteroarenes directed by a removable bidentate auxiliary. , 2014, Organic letters.

[44]  刘斌,et al.  过渡金属催化的双齿导向基辅助的惰性C（sp 3 ）—H键芳基化 , 2014 .

[45]  Fei Wang,et al.  Copper-mediated tandem oxidative C(sp2)-H/C(sp)-H alkynylation and annulation of arenes with terminal alkynes. , 2014, Organic letters.

[46]  L. Ackermann,et al.  Weakly Coordinating Directing Groups for Ruthenium(II)‐ Catalyzed CH Activation , 2014 .

[47]  Masahiro Nakano,et al.  Organic semiconductors based on [1]benzothieno[3,2-b][1]benzothiophene substructure. , 2014, Accounts of chemical research.

[48]  Yan Zhao,et al.  Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp³)-H bonds. , 2014, Angewandte Chemie.

[49]  M. Kanai,et al.  Copper-catalyzed intramolecular C(sp³)-H and C(sp²)-H amidation by oxidative cyclization. , 2014, Angewandte Chemie.

[50]  G. He,et al.  Copper-catalyzed carboxamide-directed ortho amination of anilines with alkylamines at room temperature. , 2014, Organic letters.

[51]  jin-quan yu,et al.  Cu(II)-mediated C-H amidation and amination of arenes: exceptional compatibility with heterocycles. , 2014, Journal of the American Chemical Society.

[52]  J. Carretero,et al.  Copper-catalyzed ortho-C-H amination of protected anilines with secondary amines. , 2014, Chemical communications.

[53]  Jun-Fang Gong,et al.  Copper-mediated direct aryloxylation of benzamides assisted by an N,O-bidentate directing group. , 2014, Organic letters.

[54]  P. Renaud,et al.  Thiyl radicals in organic synthesis. , 2014, Chemical reviews.

[55]  N. Chatani,et al.  Catalytic functionalization of C(sp2)-H and C(sp3)-H bonds by using bidentate directing groups. , 2013, Angewandte Chemie.

[56]  O. Daugulis,et al.  Copper-catalyzed etherification of arene C-H bonds. , 2013, Organic letters.

[57]  H. Liu,et al.  Transfer of sulfur: from simple to diverse. , 2013, Chemistry, an Asian journal.

[58]  L. Tran,et al.  Directed amination of non-acidic arene C-H bonds by a copper-silver catalytic system. , 2013, Angewandte Chemie.

[59]  K. Hirano,et al.  Copper-mediated C-H/C-H biaryl coupling of benzoic acid derivatives and 1,3-azoles. , 2013, Angewandte Chemie.

[60]  L. Tran,et al.  Copper-promoted sulfenylation of sp2 C-H bonds. , 2012, Journal of the American Chemical Society.

[61]  F. Glorius,et al.  Beyond directing groups: transition-metal-catalyzed C-H activation of simple arenes. , 2012, Angewandte Chemie.

[62]  K. Hirano,et al.  Copper-mediated oxidative direct C-C (hetero)aromatic cross-coupling. , 2012, Chemical communications.

[63]  Junichiro Yamaguchi,et al.  C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals. , 2012, Angewandte Chemie.

[64]  C. Bruneau,et al.  Ruthenium(II)-catalyzed C-H bond activation and functionalization. , 2012, Chemical reviews.

[65]  T. Mei,et al.  Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions. , 2012, Accounts of chemical research.

[66]  Fen Wang,et al.  C-C, C-O and C-N bond formation via rhodium(III)-catalyzed oxidative C-H activation. , 2012, Chemical Society reviews.

[67]  N. Jiao,et al.  Recent advances in copper-catalyzed dehydrogenative functionalization via a single electron transfer (SET) process. , 2012, Chemical Society reviews.

[68]  Alison E Wendlandt,et al.  Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights. , 2011, Angewandte Chemie.

[69]  O. Baudoin.  Transition metal-catalyzed arylation of unactivated C(sp3)-H bonds. , 2011, Chemical Society reviews.

[70]  V. Ananikov,et al.  Transition-metal-catalyzed C-S, C-Se, and C-Te bond formation via cross-coupling and atom-economic addition reactions. , 2011, Chemical reviews.

[71]  L. Ackermann.  Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope. , 2011, Chemical reviews.

[72]  Chang-Liang Sun,et al.  Direct C-H transformation via iron catalysis. , 2011, Chemical reviews.

[73]  Mao‐Lin Hu,et al.  Copper-catalyzed thiolation of the di- or trimethoxybenzene arene C-H bond with disulfides. , 2010, The Journal of organic chemistry.

[74]  F. Qing,et al.  Cu(II)-mediated methylthiolation of aryl C-H bonds with DMSO. , 2010, Organic letters.

[75]  J. Ellman,et al.  Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. , 2010, Chemical reviews.

[76]  Melanie S Sanford,et al.  Palladium-catalyzed ligand-directed C-H functionalization reactions. , 2010, Chemical reviews.

[77]  O. Daugulis,et al.  Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds. , 2009, Accounts of chemical research.

[78]  jin-quan yu,et al.  Cu(II)-mediated oxidative dimerization of 2-phenylpyridine derivatives , 2009 .

[79]  C. Bolm,et al.  Iron-catalysed carbon-heteroatom and heteroatom-heteroatom bond forming processes. , 2008, Chemical Society reviews.

[80]  M. Mellah,et al.  Chiral sulfur ligands for asymmetric catalysis. , 2007, Chemical reviews.

[81]  John E Anthony,et al.  Functionalized acenes and heteroacenes for organic electronics. , 2006, Chemical reviews.

[82]  Jeffrey T. Kuethe,et al.  Practical methodologies for the synthesis of indoles. , 2006, Chemical reviews.

[83]  jin-quan yu,et al.  Cu(II)-catalyzed functionalizations of aryl C-H bonds using O2 as an oxidant. , 2006, Journal of the American Chemical Society.

[84]  Andrea Brancale,et al.  New arylthioindoles: potent inhibitors of tubulin polymerization. 2. Structure-activity relationships and molecular modeling studies. , 2006, Journal of medicinal chemistry.

[85]  O. Daugulis,et al.  Highly regioselective arylation of sp3 C-H bonds catalyzed by palladium acetate. , 2005, Journal of the American Chemical Society.

[86]  Yiyun Huang,et al.  Fluorinated diaryl sulfides as serotonin transporter ligands: synthesis, structure-activity relationship study, and in vivo evaluation of fluorine-18-labeled compounds as PET imaging agents. , 2005, Journal of medicinal chemistry.

[87]  S. Ley,et al.  Modern Synthetic Methods for Copper‐Mediated C(aryl) ? O, C(aryl) ? N, and C(aryl) ? S Bond Formation , 2003 .

[88]  T. Mitsudo,et al.  Metal-catalyzed carbon-sulfur bond formation. , 2000 .