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Simple Synthesis of Benzazoles by Substrate-Promoted CuI-Catalyzed Aerobic Oxidative Cyclocondensation of o-Thio/Amino/Hydroxyanilines and Amines under Air

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Abstract

By catalyst and condition screening, a simple method for the synthesis of benzazole and quinoxaline heterocycles via Cu-catalyzed direct aerobic oxidative cyclocondensation of o-thio/hydroxy/aminoanilines and amines was developed by using air as the safe, cheap, effective, and clean oxidant. Due to the observed great promoting effect of the substrates on the reaction, single CuI can be used as the efficient catalyst without requiring additional oxidation co-catalysts. This method provides a simple and practical way for preparation of the useful benzothiazoles, benzimidazoles and benzoxazoles from amines.

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Notes

  1. For selected examples, see: [11–20]

  2. For selected examples, see: [23–35]

  3. For selected examples, see: [45–48]

  4. Different to the reaction with 2-aminobenzenethiol 2a, the reaction of the 2-phenylethylamine 1o with o-diaminobenzene 4a is successful for quinoxaline derivative synthesis. See Eq. 5.

  5. See the Supporting Information for details

  6. How o-substituted anilines promoted the aerobic amine oxidation step is not exactly clear at present; whereas, according to aerobic amine oxidation reactions catalyzed by quinine-type catalysts [99–105], it is very possible that the reactions proceed via analogous o-iminothioquinone-type catalytic species. For reviews and reports: [55, 56, 99–105].

References

  1. Wright JB (1951) Chem Rev 48:397

    Article  CAS  Google Scholar 

  2. Tamm I (1954) Science 120:847

    Article  CAS  Google Scholar 

  3. Preston PN (1974) Chem Rev 74:279

    Article  CAS  Google Scholar 

  4. Weissberger A, Taylor EC (1981) The chemistry of heterocyclic compounds, Part I, vol 40. Wiley, New York

  5. Katrizky AR, Rees CW (1984) Comprehensive heterocyclic chemistry, vol 5. Pergamon, Oxford

  6. Katritzky AR, Rees CW, Scriven EF (1999) Comprehensive heterocyclic chemistry III, vol 1. Pergamon, Oxford

    Google Scholar 

  7. Katritzky A, Pozharskii A (2003) Handbook of Heterocyclic chemistry, 1st edn. Pergamon, Oxford

    Google Scholar 

  8. Candeias NR, Branco LC, Gois PMP, Afonso CAM, Trindade AF (2009) Chem Rev 109:2703

    Article  CAS  Google Scholar 

  9. Asensio JA, Sanchez EM, Gomez-Romero P (2010) Chem Soc Rev 39:3210

    Article  CAS  Google Scholar 

  10. Carvalho LCR, Fernandes E, Marques MMB (2011) Chem Eur J 17:12544

    Article  CAS  Google Scholar 

  11. Holljes ELJ, Wagner EC (1944) J Org Chem 9:31

    Article  CAS  Google Scholar 

  12. Sandera G, Isensee RW, Joseph L (1954) J Am Chem Soc 76:5173

    Article  CAS  Google Scholar 

  13. Hein DW, Alheim RJ, Leavitt JJ (1957) J Am Chem Soc 79:427

    Article  CAS  Google Scholar 

  14. Hendrickson JB, Hussoin MS (1987) J Org Chem 52:4137

    Article  Google Scholar 

  15. So Y-H, Heeschen JP (1997) J Org Chem 62:3552

    Article  CAS  Google Scholar 

  16. Lim H-J, Myung D, Lee IYC, Jung MH (2008) J Comb Chem 10:501

    Article  CAS  Google Scholar 

  17. Thomas OD, Soo KJWY, Peckham TJ, Kulkarni MP, Holdcroft S (2012) J Am Chem Soc 134:10753

    Article  CAS  Google Scholar 

  18. Panda SS, Ibrahim MA, Oliferenko AA, Asiri AM, Katritzky AR (2013) Green Chem 15:2709

    Article  CAS  Google Scholar 

  19. Sun Y, Jiang H, Wu W, Zeng W, Wu X (2013) Org Lett 15:1598

    Article  CAS  Google Scholar 

  20. Bommegowda YK, Lingaraju GS, Thamas S, Kumar KSV, Kumara CSP, Rangappa KS, Sadashiva MP (2013) Tetrahedron Lett 54:2693

    Article  CAS  Google Scholar 

  21. Qiao JX, Wang TC, Hu C, Li J, Wexler RR, Lam PYS (2011) Org Lett 13:1804

    Article  CAS  Google Scholar 

  22. Siddappa C, Kambappa V, Umashankara M, Rangappa KS (2011) Tetrahedron Lett 52:5474

    Article  CAS  Google Scholar 

  23. Kawashita Y, Nakamichi N, Kawabata H, Hayashi M (2013) Org Lett 5:3713

    Article  CAS  Google Scholar 

  24. Chakraborti AK, Rudrawar S, Jadhav KB, Kaur G, Chankeswara SV (2007) Green Chem 9:1335

    Article  CAS  Google Scholar 

  25. Chen YX, Qian IF, Zhang W, Han B (2008) Angew Chem Int Ed 47:9330

    Article  CAS  Google Scholar 

  26. Bahrami K, Khodaei MM, Naali F (2008) J Org Chem 73:6835

    Article  CAS  Google Scholar 

  27. Osowska K, Miljanić OŠ (2011) J Am Chem Soc 133:724

    Article  CAS  Google Scholar 

  28. Parikh N, Kumar D, Roy SR, Chakraborti AK (2011) Chem Commun 47:1797

    Article  CAS  Google Scholar 

  29. Zhang C, Zhang L, Jiao N (2012) Green Chem 14:3273

    Article  CAS  Google Scholar 

  30. Chebolu R, Kommi DN, Kumar D, Bollineni N, Chakraborti AK (2012) J Org Chem 77:10158

    Article  CAS  Google Scholar 

  31. Cho YH, Lee C-Y, Ha D-C, Cheon C-H (2012) Adv Synth Catal 354:2992

    Article  CAS  Google Scholar 

  32. Samanta S, Das S, Biswas P (2013) J Org Chem 78:11184

    Article  CAS  Google Scholar 

  33. Chen S, Hossain MS, Foss FW Jr (2013) ACS Sustainable Chem Eng 1:1045

    Article  CAS  Google Scholar 

  34. Lirag RC, Le HTM, Miljanic OS (2013) Chem Commun 49:4304

    Article  CAS  Google Scholar 

  35. Yu C, Lee K, You Y, Choa EJ (2013) Adv Synth Catal 355:1471

    Article  CAS  Google Scholar 

  36. Evindar G, Batey RA (2006) J Org Chem 71:1802

    Article  CAS  Google Scholar 

  37. Vera MD, Pelletier JC (2007) J Comb Chem 9:569

    Article  CAS  Google Scholar 

  38. Itoh T, Mase T (2007) Org Lett 9:3687

    Article  CAS  Google Scholar 

  39. Zou B, Yuan Q, Ma D (2007) Angew Chem Int Ed 46:2598

    Article  CAS  Google Scholar 

  40. Bonnamour J, Bolm C (2008) Org Lett 10:2665

    Article  CAS  Google Scholar 

  41. Ma D, Xie S, Xue P, Zhang X, Dong J, Jiang Y (2009) Angew Chem Int Ed 48:4222

    Article  CAS  Google Scholar 

  42. Peng J, Ye M, Zong C, Hu F, Feng L, Wang X, Wang Y, Chen C (2011) J Org Chem 76:716

    Article  CAS  Google Scholar 

  43. Baars H, Beyer A, Kohlhepp SV, Bolm C (2014) Org Lett 16:536

    Article  CAS  Google Scholar 

  44. Zhang G, Liu C, Yi H, Meng Q, Bian C, Chen H, Jian J-X, Wu L-Z, Lei A (2015) J Am Chem Soc 137:9273

    Article  CAS  Google Scholar 

  45. Kondo T, Yang S, Huh K-T, Kobayashi M, Kotachi S, Watanabe Y (1991) Chem Lett 1991:1275

    Article  Google Scholar 

  46. Huh K-T, Shim SC (1993) Bull Korean Chem Soc 14:449

    CAS  Google Scholar 

  47. Blacker AJ, Farah MM, Hall MI, Marsden SP, Saidi O, Williams JMJ (2009) Org Lett 11:2039

    Article  CAS  Google Scholar 

  48. Shiraishi Y, Sugano Y, Tanaka S, Hirai T (2010) Angew Chem Int Ed 49:1656

    Article  CAS  Google Scholar 

  49. Murahashi S-I, Naota T, Taki H (1985) Chem Commun 1985:613

    Article  Google Scholar 

  50. Müller P, Gilabert DM (1988) Tetrahedron 44: 7171

  51. Ell AH, Samec JS, Brasse C, Backvall J-E (2002) Chem Commun 2002:1144

    Article  CAS  Google Scholar 

  52. Nicolaou KC, Mathison CJN, Montagnon T (2003) Angew Chem Int Ed 42:4077

    Article  CAS  Google Scholar 

  53. Nicolaou KC, Mathison CJN, Montagnon T (2004) J Am Chem Soc 126:5192

    Article  CAS  Google Scholar 

  54. Choi H, Doyle MP (2007) Chem Commun 2007:745

    Article  CAS  Google Scholar 

  55. Largeron M, Fleury MB (2013) Science 339:43

    Article  Google Scholar 

  56. Largeron M, Fleury MB (2012) Angew Chem Int Ed 51:5409

    Article  CAS  Google Scholar 

  57. Patil RD, Adimurthy S (2011) Adv Synth Catal 353:1695

    Article  CAS  Google Scholar 

  58. Hu Z, Kerton FM (2012) Org Biomol Chem 10:1618

    Article  CAS  Google Scholar 

  59. Muthaiah S, Hong SK (2012) Adv Synth Catal 354:3045

    Article  CAS  Google Scholar 

  60. Prades A, Peris E, Albrecht M (2011) Organometallics 30:1162

    Article  CAS  Google Scholar 

  61. Yi CS, Lee DW (2009) Organometallics 28: 947

  62. Huang B, Tian H, Lin S, Xie M, Yu X, Xu Q (2013) Tetrahedron Lett 54:2861

    Article  CAS  Google Scholar 

  63. Zhang E, Tian H, Xu S, Yu X, Xu Q (2013) Org Lett 15:2704

    Article  CAS  Google Scholar 

  64. Nguyen TB, Bescont JL, Ermolenko L, Al-Mourabit A (2013) Org Lett 15:6218

    Article  CAS  Google Scholar 

  65. Tong Y, Pan Q, Jiang Z, Miao D, Shi X, Han S (2014) Tetrahedron Lett 55:5499

    Article  CAS  Google Scholar 

  66. Nguyen TB, Ermolenko L, Retailleau P, Al-Mourabit A (2014) Angew Chem Int Ed 53:13808

    Article  CAS  Google Scholar 

  67. Sarode SA, Bhojane JM, Nagarkar JM (2015) Tetrahedron Lett 56:206

    Article  CAS  Google Scholar 

  68. Wang R, Ding Y-L, Liu H, Peng S, Ren J, Li L (2014) Tetrahedron Lett 55:945

    Article  CAS  Google Scholar 

  69. Blacker AJ, Farah MM, Marsden SP, Saidi O, Williams JMJ (2009) Tetrahedron Lett 50:6106

    Article  CAS  Google Scholar 

  70. Jin X, Liu Y, Lu Q, Yang D, Sun J, Qin S, Zhang J, Shen J, Chang C, Liu R (2013) Org Biomol Chem 11:3776

    Article  CAS  Google Scholar 

  71. Nguyen TB, Ermolenko L, Dean WA, Al-Mourabit A (2012) Org Lett 14:5948

    Article  CAS  Google Scholar 

  72. Naresh G, Kant R, Narender T (2014) J Org Chem 79:3821

    Article  CAS  Google Scholar 

  73. Yu J, Lu M (2014) Synth Commun 44:2520

    Article  CAS  Google Scholar 

  74. Su F, Mathew SC, Möhlmann L, Antonietti M, Wang X, Blechert S (2011) Angew Chem Int Ed 50:657

    Article  CAS  Google Scholar 

  75. Nguyen TB, Ermolenko L, Al-Mourabit A (2013) Green Chem 15:2713

    Article  CAS  Google Scholar 

  76. Gopalaiah K, Chandrudu SN (2015) RSC Adv 5:5015

    Article  CAS  Google Scholar 

  77. Chen X, Chen T, Zhou Y, Han D, Han L-B, Yin S-F (2014) Org Biomol Chem 12:3802

    Article  CAS  Google Scholar 

  78. Endo Y, Bäckvall J-E (2012) Chem-Eur J 18:13609

    Article  CAS  Google Scholar 

  79. Xiao T, Xiong S, Xie Y, Dong X, Zhou L (2013) RSC Adv 3:15592

    Article  CAS  Google Scholar 

  80. Su C, Tandiana R, Balapanuru J, Tang W, Pareek K, Nai CT, Hayashi T, Loh KP (2015) J Am Chem Soc 137:685

    Article  CAS  Google Scholar 

  81. Nguyen KMH, Largeron M (2015) Chem-Eur J 21:12606

    Article  CAS  Google Scholar 

  82. Liu C, Liao S, Li Q, Feng S, Sun Q, Yu X, Xu Q (2011) J Org Chem 76:5759

    Article  CAS  Google Scholar 

  83. Yu X, Jiang L, Li Q, Xie Y, Xu Q (2012) Chin J Chem 30:2322

    Article  CAS  Google Scholar 

  84. Yu X, Liu C, Jiang L, Xu Q (2011) Org Lett 13:6184

    Article  CAS  Google Scholar 

  85. Li Q, Fan S, Sun Q, Tian H, Yu X, Xu Q (2012) Org Biomol Chem 10:2966

    Article  CAS  Google Scholar 

  86. Liao S, Yu K, Li Q, Tian H, Zhang Z, Yu X, Xu Q (2012) Org Biomol Chem 10:2973

    Article  CAS  Google Scholar 

  87. Jiang L, Jin L, Tian H, Yuan X, Yu X, Xu Q (2011) Chem Commun 47:10833

    Article  CAS  Google Scholar 

  88. Tian H, Yu X, Li Q, Wang J, Xu Q (2012) Adv Synth Catal 354:2671

    Article  CAS  Google Scholar 

  89. Xu Q, Huang X, Yuan J (2005) J Org Chem 70:6948

    Article  CAS  Google Scholar 

  90. Yu L, Wu Y, Chen T, Pan Y, Xu Q (2013) Org Lett 15:144

    Article  CAS  Google Scholar 

  91. Yu L, Wu Y, Cao H, Zhang X, Shi X, Luan J, Chen T, Pan Y, Xu Q (2014) Green Chem 16:287

    Article  CAS  Google Scholar 

  92. Li Q, Huang Y, Chen T, Zhou Y, Xu Q, Yin S-F, Han L-B (2014) Org Lett 16:3672

    Article  CAS  Google Scholar 

  93. Shi X, Guo J, Liu J, Ye M, Xu Q (2015) Chem-Eur J 21:9988

    Article  CAS  Google Scholar 

  94. Yu L, Liu M, Chen F, Xu Q (2015) Org Biomol Chem 13:8379

    Article  CAS  Google Scholar 

  95. Li S, Li X, Li Q, Yuan Q, Shi X, Xu Q (2015) Green Chem 17:3260

    Article  CAS  Google Scholar 

  96. Jia X, Yu L, Liu J, Xu Q, Sickert M, Chen L, Lautens M (2014) Green Chem 16:3444

    Article  CAS  Google Scholar 

  97. Liu Q, Lu Z, Ren W, Shen K, Wang Y, Xu Q (2013) Chin J Chem 31:764

    Article  CAS  Google Scholar 

  98. Liu C, Zang X, Yu B, Yu X, Xu Q (2011) Synlett 2011:1143

    Article  CAS  Google Scholar 

  99. Wendlandt AE, Stahl SS (2015) Angew Chem Int Ed 54:14638

    Article  CAS  Google Scholar 

  100. Wendlandt AE, Stahl SS (2012) Org Lett 14:2850

    Article  CAS  Google Scholar 

  101. Yuan H, Yoo W-J, Miyamura H, Kobayashi S (2012) J Am Chem Soc 134:13970

    Article  CAS  Google Scholar 

  102. Yuan H, Yoo W-J, Miyamura H, Kobayashi S (2012) Adv Synth Catal 354:2899

    Article  CAS  Google Scholar 

  103. Wendlandt AE, Stahl SS (2014) J Am Chem Soc 136:506

    Article  CAS  Google Scholar 

  104. Wendlandt AE, Stahl SS (2014) J Am Chem Soc 136:11910

    Article  CAS  Google Scholar 

  105. Qin Y, Zhang L, Lv J, Luo S, Cheng J-P (2015) Org Lett 17:1469

    Article  CAS  Google Scholar 

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Acknowledgments

We thank ZJNSF for Distinguished Young Scholars (LR14B020002), China Postdoctoral Science Foundation (2016M592520), and NNSFC (21502143) for financial support.

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Authors and Affiliations

  1. College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035, People’s Republic of China

    Jianping Liu, Chao Wang, Xiantao Ma, Xinkang Shi, Xin Wang, Huan Li & Qing Xu

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  1. Jianping Liu
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  2. Chao Wang
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  3. Xiantao Ma
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  4. Xinkang Shi
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  5. Xin Wang
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Correspondence to Jianping Liu or Qing Xu.

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Liu, J., Wang, C., Ma, X. et al. Simple Synthesis of Benzazoles by Substrate-Promoted CuI-Catalyzed Aerobic Oxidative Cyclocondensation of o-Thio/Amino/Hydroxyanilines and Amines under Air. Catal Lett 146, 2139–2148 (2016). https://doi.org/10.1007/s10562-016-1818-2

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