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Photoinduced C-H direct arylation of unactivated arenes

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Abstract

Two general protocols have been developed for the photoinduced, metal-free direct arylation of unactivated arenes with aryl iodide. Both methods gave good to excellent yields for most substrates. Notably, the C-F bond in method A and the C-F, C-Cl, and C-Br bonds in method B could survive the arylation reaction. These methods offered excellent options for syntheses of biaryls.

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References

  1. Evans DA, Dinsmore CJ, Watson PS, Wood MR, Richardson TI, Trotter BW, Katz JL. Nonconventional stereochemical issues in the design of the synthesis of the vancomycin antibiotics: challenges imposed by axial and nonplanar chiral elements in the heptapeptide aglycons. Angew Chem Int Ed, 1998, 37: 2704–2708

    Article  CAS  Google Scholar 

  2. Cuccia LA, Lehn JM, Homo JC, Schmutz M. Encoded helical self-organization and self-assembly into helical fibers of an oligoheterocyclic pyridine-pyridazine molecular strand. Angew Chem Int Ed, 2000, 39: 233–237

    Article  CAS  Google Scholar 

  3. Lehn JM. Toward self-organization and complex matter. Science, 2002, 295: 2400–2403

    Article  CAS  Google Scholar 

  4. Laird T. What type of reactions do process chemists use on scale? Org Process Res Dev, 2006, 10: 851–852

    Article  CAS  Google Scholar 

  5. Corbet JP, Mignani G. Selected patented cross-coupling reaction technologies. Chem Rev, 2006, 106: 2651–2710

    Article  CAS  Google Scholar 

  6. de Meijere A, Diederich F. Metal-Catalyzed Cross-Coupling Reactions. 2nd Ed. Weinheim: Wiley-VCH, 2004

    Book  Google Scholar 

  7. Miyaura N. Cross-Coupling Reactions. Topics in Current Chemistry. Berlin: Springer, 2002

    Book  Google Scholar 

  8. Tsuji J. Transition Metal Reagents and Catalysts: Innovaions in Organic Synthesis. Chichester: Wiley, 2002

    Book  Google Scholar 

  9. Hartwig JF. Organotransition Metal Chemistry: From Bonding to Catalysis. Sauaslito: University Science Book, 2010

    Google Scholar 

  10. MacMillan DWC. The advent and development of organocatalysis. Nature, 2008, 455: 304–308

    Article  CAS  Google Scholar 

  11. Bertelsen S, Jorgensen KA. Organocatalysis: after the gold rush. Chem Soc Rev, 2009, 38: 2178–2189

    Article  CAS  Google Scholar 

  12. For rencent reviews, see: (a) Studer A, Curran DP. Organocatalysis and C–H activation meet radical- and electron-transfer reactions. Angew Chem Int Ed, 2011, 50: 5018–5022

    Article  CAS  Google Scholar 

  13. Yanagisawa S, Itami K. tert-Butoxide-mediated C–H bond arylation of aromatic compounds with haloarenes. ChemCatChem, 2011, 3: 827–829

    Article  CAS  Google Scholar 

  14. Shirakawa E, Hayashi T. Transition-metal-free coupling reactions of aryl halides. Chem Lett, 2012, 41: 130–134

    Article  CAS  Google Scholar 

  15. Chan TL, Wu Y, Choy PY, Kwong FY. A radical process towards the development of transitionmetal-free aromatic carbon-carbon bond-forming reactions. Chem Eur J, 2013, 19: 15802

    Article  CAS  Google Scholar 

  16. Sun CL, Shi ZJ. Transition-metal-free coupling reactions. Chem Rev, 2014, 114: 9219–9280

    Article  CAS  Google Scholar 

  17. Yanagisawa S, Ueda K, Taniguchi T, Itami K. Potassium t-butoxide alone can promote the biaryl coupling of electron-deficient nitrogen heterocycles and haloarenes. Org Lett, 2008, 10: 4673–4676

    Article  CAS  Google Scholar 

  18. Shirakawa E, Itoh K, Higashino T, Hayashi T. tert-Butoxidemediated arylation of benzene with aryl halides in the presence of a catalytic 1,10-phenanthroline derivative. J Am Chem Soc, 2010: 132, 15537–15539

    Article  CAS  Google Scholar 

  19. Sun CL, Li H, Yu DG, Yu M, Zhou X, Lu XY, Huang K, Zheng SF, Li BJ, Shi ZJ. An efficient organocatalytic method for constructing biaryls through aromatic C–H activation. Nat Chem, 2010, 2: 1044–1049

    Article  CAS  Google Scholar 

  20. Liu W, Cao H, Zhang H, Chung KH, He C, Wang H, Kwong FY, Lei AW. Organocatalysis in crosscoupling: DMEDA-catalyzed direct C–H arylation of unactivated benzene. J Am Chem Soc, 2010, 132: 16737–16740

    Article  CAS  Google Scholar 

  21. Qiu Y, Liu Y, Yang K, Hong W, Li Z, Wang Z, Yao Z, Jiang S. New ligands that promote cross-coupling reactions between aryl halides and unactivated arenes. Org Lett, 2011, 13: 3556–3559

    Article  CAS  Google Scholar 

  22. Yong GP, She WL, Zhang YM, Li YZ. Direct arylation of unactivated aromatic C–H bonds catalyzed by a stable organic radical. Chem Commun, 2011, 47: 11766–11768

    Article  CAS  Google Scholar 

  23. Rueping M, Leiendecker M, Das A, Poisson T, Bui L. Potassium tert-butoxide mediated Hecktype cyclization/isomerization-benzofurans from organocatalytic radical cross-coupling reactions. Chem Commun, 2011, 47: 10629–10631

    Article  CAS  Google Scholar 

  24. Vakuliuk O, Koszarna B, Gryko DT. Base-mediated direct arylation of pyrrole derivatives. Adv Synth Catal, 2011, 353: 925–930

    Article  CAS  Google Scholar 

  25. Roman DS, Takahashi Y, Charette AB. Potassium tert-butoxide promoted intramolecular arylation via a radical pathway. Org Lett, 2011, 13: 3242–3245

    Article  CAS  Google Scholar 

  26. Liu H, Yin B, Gao Z, Li Y, Jiang H. Transition-metal-free highly chemo- and regioselective arylation of unactivated arenes with aryl halides over recyclable heterogeneous catalysts. Chem Commun, 2012, 48: 203–-2035

    Article  Google Scholar 

  27. Chen WC, Hsu YC, Shih WC, Lee CY, Chuang WH, Tsai YF, Chen PY, Ong TG. Metalfree arylation of benzene and pyridine promoted by amino-linked nitrogen heterocyclic carbenes. Chem Commun, 2012, 48: 6702–6704

    Article  CAS  Google Scholar 

  28. Zhao HQ, Shen J, Guo JJ, Ye RJ, Zeng HQ. A macrocyclic aromatic pyridone pentamer as a highly efficient organocatalyst for the direct arylations of unactivated arenes. Chem Commun, 2013, 49: 2323–2325

    Article  CAS  Google Scholar 

  29. Truong T, Daugulis O. Base-mediated intermolecular sp2 C–H bond arylation via benzyne intermediates. J Am Chem Soc, 2011, 133: 4243–4245

    Article  CAS  Google Scholar 

  30. Prier CK, Rankic DA, MacMillan DWC. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. Chem Rev, 2013, 113: 5322–5363

    Article  CAS  Google Scholar 

  31. Narayanam JMR, Stephenson CRJ. Visible light photoredox catalysis: applications in organic synthesis. Chem Soc Rev, 2011, 40: 102–113

    Article  CAS  Google Scholar 

  32. Nagib DA, MacMillan DWC. Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis. Nature, 2011, 480: 224–228

    Article  CAS  Google Scholar 

  33. Ye Y, Sanford MS. Merging visible-light photocatalysis and transition-metal catalysis in the copper-catalyzed trifluoromethylation of boronic acids with CF3I. J Am Chem Soc, 2012, 134: 9034–9037

    Article  CAS  Google Scholar 

  34. Schroll P, Hari DP, König B. Photocatalytic arylation of alkenes, alkynes and enones with diazonium salts. ChemistryOpen, 2012, 1: 130–133

    Article  CAS  Google Scholar 

  35. Yasu Y, Koike T, Akita M. Three-component oxytrifluoromethylation of alkenes: highly efficient and regioselective difunctionalization of C=C bonds mediated by photoredox catalysts. Angew Chem Int Ed, 2012, 51: 9567–9571

    Article  CAS  Google Scholar 

  36. Nguyen JD, Tucker JW, Konieczynska MD, Stephenson CRJ. Intermolecular atom transfer radical addition to olefins mediated by oxidative quenching of photoredox catalysts. J Am Chem Soc, 2011, 133: 4160–4163

    Article  CAS  Google Scholar 

  37. Tucker JW, Nguyen JD, Narayanam JMR, Krabbe SW, Stephenson CRJ. Tin-free radical cyclization reactions initiated by visible light photoredox catalysis. Chem Commun, 2010, 46: 4985–4987

    Article  CAS  Google Scholar 

  38. Kim H, Lee C. Visible-light-induced photocatalytic reductive transformations of organohalides. Angew Chem Int Ed, 2012, 51: 12303–12306

    Article  CAS  Google Scholar 

  39. Zou YQ, Chen JR, Xiao WJ. Homogeneous visible-light photoredox catalysis. Angew Chem Int Ed, 2013, 52: 11701–11703

    Article  CAS  Google Scholar 

  40. Baralle A, Fensterbank L, Goddard JP, Ollivier C. Aryl radical formation by copper(I) photocatalyzed reduction of diaryliodonium salts: NMR evidence for a Cu(II)/Cu(I) mechanism. Chem Eur J, 2013, 19: 10809–10813

    Article  CAS  Google Scholar 

  41. Xue QC, Xie J, Jin HM, Cheng YX, Zhu CJ. Highly efficient visible-light-induced aerobic oxidative C–C, C–P coupling from C–H bonds catalyzed by a gold(III)-complex. Org Biomol Chem, 2013, 11: 1606–1609

    Article  CAS  Google Scholar 

  42. Willis MC, Hicke BJ, Uhlenbeck OC, Cech TR, Koch TH. Photocrosslinking of 5-iodouracil-substituted RNA and DNA to proteins. Science, 1993, 262: 1255–1257

    Article  CAS  Google Scholar 

  43. Hari DP, Schroll P, König B. Metal-free, visible-light-mediated direct C–H arylation of heteroarenes with aryl diazonium salts. J Am Chem Soc, 2012, 134: 2958–2961

    Article  CAS  Google Scholar 

  44. Kalyani D, McMurtrey KB, Neufeldt SR. Sanford MS. Room-temperature C–H arylation: merger of Pd-catalyzed C–H functionalization and visible-light photocatalysis. J Am Chem Soc, 2011, 133: 18566–18569

    Article  CAS  Google Scholar 

  45. Liu YX, Xue D, Wang JD, Zhao CJ, Zou QZ, Wang C, Xiao JL. Room-temperature arylation of arenes and heteroarenes with diaryliodonium salts by photoredox catalysis. Synlett, 2013, 24: 507–513

    Article  CAS  Google Scholar 

  46. Sharma RK, Kharach N. The photolysis of iodoaromatic compounds. Angew Chem Int Ed, 1968, 7: 36–44

    Article  CAS  Google Scholar 

  47. De Carolis MD, Protti S, Fagnoni M, Albini A. Metal-free cross-coupling reactions of aryl sulfonates and phosphates through photoheterolysis of aryloxygen bonds. Angew Chem, 2005, 117: 1232–1236

    Article  Google Scholar 

  48. Dichiarante V, Fagnoni M, Albini A. Metal-free synthesis of sterically crowded biphenyls by direct Ar–H substitution in alkyl benzenes. Angew Chem Int Ed, 2007, 46: 6495–6498

    Article  CAS  Google Scholar 

  49. verga D, Doria F, Pretali L, Freccero M. Photoarylation of alkenes and heteroaromatics by dibromo-BINOLs in aqueous solution. J Org Chem, 2010, 75: 3477–3480

    Article  CAS  Google Scholar 

  50. Linsenmeier AM. Williams CM, Bräse S. Synthesis of phenanthridine derivatives via photolysis. J Org Chem, 2011, 76: 9127–9132

    Article  CAS  Google Scholar 

  51. Budén ME, Guastavino JF, Rossi RA. Room-temperature photoinduced direct C–H–arylation via base-promoted homolytic aromatic substitution. Org Lett, 2013, 15: 1174–1177

    Article  Google Scholar 

  52. Zheng XL, Yang L, Du WY, Ding AS, Guo H. Amine-catalyzed direct photoarylation of unactivated arenes. Chem Asian J, 2014, 9: 439–442

    Article  CAS  Google Scholar 

  53. Cheng YN, Gu XY, Li PX. Visible-light photoredox in homolytic aromatic substitution: direct arylation of arenes with aryl halides. Org Lett, 2013, 15: 2664–2667

    Article  CAS  Google Scholar 

  54. Schmidt LC, Arguello JE, Penenory AB. Nature of the chain propagation in the photostimulated reaction of 1-bromonaphthalene with sulfur-centered nucleophiles. J Org Chem, 2007, 72: 2936–2944

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry; Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Jian Kan, Shijun Huang, Huaiqing Zhao, Jin Lin & Weiping Su

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  1. Jian Kan
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  2. Shijun Huang
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Correspondence to Weiping Su.

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Kan, J., Huang, S., Zhao, H. et al. Photoinduced C-H direct arylation of unactivated arenes. Sci. China Chem. 58, 1329–1333 (2015). https://doi.org/10.1007/s11426-015-5377-y

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