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Free-Radical Synthesis and Functionalization of Heterocycles pp 93–149Cite as

Free Radicals in Heterocycle Functionalization

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Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 54))

Abstract

Functionalization of heterocycles through free radical intermediates has been widely employed in a diverse array of synthetic transformations. This chapter focuses on the recent developments in the light-assisted as well as traditional free radical generation methodology and the subsequent utilization in functionalization of various heterocycles.

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References

  1. Nicewicz D, MacMillan DWC (2008) Science 322:77–80

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. Prier CK, Rankic DA, MacMillan DWC (2013) Chem Rev 113:5322–5363

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Tauber J, Imbri D, Opatz T (2014) Molecules 19:16190–16222

    Article  PubMed  CAS  PubMed Central  Google Scholar 

  4. Minisci F (1973) Synthesis 1973:1–24

    Article  Google Scholar 

  5. Punta C, Minisci F (2008) Trends Heterocycl Chem 13:1–68

    CAS  Google Scholar 

  6. Twilton J, Le CC, Zhang P, Shaw MH, Evans RW, MacMillan DWC (2017) Nat Chem Rev 1:0052

    Article  CAS  Google Scholar 

  7. McNally A, Prier CK, MacMillan DWC (2011) Science 334:1114–1117

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Miyake Y, Nakajima K, Nishibayashi Y (2012) J Am Chem Soc 134:3338–3341

    Article  CAS  PubMed  Google Scholar 

  9. Kohls P, Jadhav D, Pandey G, Reiser O (2012) Org Lett 14:672–675

    Article  CAS  PubMed  Google Scholar 

  10. Espelt LR, Wiensch EM, Yoon TP (2013) J Org Chem 78:4107–4114

    Article  PubMed Central  CAS  Google Scholar 

  11. Hager D, MacMillan DWC (2014) J Am Chem Soc 136:16986–16989

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Heitz DR, Tellis JC, Molander GA (2016) J Am Chem Soc 138:12715–12718

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Shields BJ, Doyle AG (2016) J Am Chem Soc 138:12719–12722

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. Joe CL, Doyle AG (2016) Angew Chem Int Ed 55:4040–4043

    Article  CAS  Google Scholar 

  15. Xuan J, Zeng TT, Feng ZJ, Deng QH, Chen JR, Lu LQ, Xiao WJ, Alper H (2015) Angew Chem Int Ed 54:1625–1628

    Article  CAS  Google Scholar 

  16. Shaw MH, Shurtleff VW, Terrett JA, Cuthbertson JD, MacMillan DWC (2016) Science 352:1304–1308

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Zuo Z, MacMillan DWC (2014) J Am Chem Soc 136:5257–5260

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Chu L, Ohta C, Zuo Z, MacMillan DWC (2014) J Am Chem Soc 136:10886–10889

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Noble A, MacMillan DWC (2014) J Am Chem Soc 136:11602–11605

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Zuo Z, Ahneman DT, Chu L, Terrett JA, Doyle AG, MacMillan DWC (2014) Science 345:437–440

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Noble A, McCarver SJ, MacMillan DWC (2015) J Am Chem Soc 137:624–627

    Article  CAS  PubMed  Google Scholar 

  22. Matsui JK, Molander GA (2017) Org Lett 19:436–439

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  23. Zhang P, Le CC, MacMillan DWC (2016) J Am Chem Soc 138:8084–8087

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Manna S, Antonchick AP (2015) Angew Chem Int Ed 54:14845–14848

    Article  CAS  Google Scholar 

  25. Liang Z, Xu S, Tian W, Zhang R (2015) Beilstein J Org Chem 11:425–430

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Guo JT, Yang DC, Guan Z, He YH (2017) J Org Chem 82:1888–1894

    Article  CAS  PubMed  Google Scholar 

  27. Yadav AK, Yadav LDS (2017) Tetrahedron Lett 58:552–555

    Article  CAS  Google Scholar 

  28. Song Z, Antonchick AP (2016) Tetrahedron 72:7715–7721

    Article  CAS  Google Scholar 

  29. Yadav AK, Yadav LDS (2016) Tetrahedron Lett 57:1489–1491

    Article  CAS  Google Scholar 

  30. Duncton MAJ (2011) Med Chem Commun 2:1135–1161

    Article  CAS  Google Scholar 

  31. Molander GA, Colombel V, Braz VA (2011) Org Lett 13:1852–1855

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  32. Presset M, Fleury-Bregeot N, Oehlrich D, Rombouts F, Molander GA (2013) J Org Chem 78:4615–4619

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Li GX, Morales-Rivera CA, Wang Y, Gao F, He G, Liu P, Chen G (2016) Chem Sci 7:6407–6412

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  34. Seiple IB, Su S, Rodriguez RA, Gianatassio R, Fujiwara Y, Sobel AL, Baran PS (2010) J Am Chem Soc 132:13194–13196

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  35. Modak A, Rana S, Maiti D (2015) J Org Chem 80:296–303

    Article  CAS  PubMed  Google Scholar 

  36. Wang J, Wang S, Wang G, Zhang J, Yu XQ (2012) Chem Commun 48:11769–11771

    Article  CAS  Google Scholar 

  37. Thatikonda T, Singh U, Ambala S, Vishwakarma RA, Singh PP (2016) Org Biomol Chem 14:4312–4320

    Article  CAS  PubMed  Google Scholar 

  38. Nagib DA, MacMillan DWC (2011) Nature 480:224–228

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Beatty JW, Douglas JJ, Cole KP, Stephenson CRJ (2015) Nat Commun 6:7919

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  40. Beatty JW, Douglas JJ, Miller R, McAtee RC, Cole KP, Stephenson CRJ (2016) Chem 1:456–472

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  41. Douglas JJ, Albright H, Sevrin MJ, Cole KP, Stephenson CRJ (2015) Angew Chem Int Ed 54:14898–14902

    Article  CAS  Google Scholar 

  42. Su YM, Hou Y, Yin F, Xu YM, Li Y, Zheng X, Wang XS (2014) Org Lett 16:2958–2961

    Article  CAS  PubMed  Google Scholar 

  43. Pitre SP, McTiernan CD, Ismaili H, Scaiano JC (2014) ACS Catal 4:2530–2535

    Article  CAS  Google Scholar 

  44. Ji Y, Brueckl T, Baxter RD, Fujiwara Y, Seiple IB, Su S, Blackmond DG, Baran PS (2011) Proc Natl Acad Sci 108:14411–14415

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  45. Fujiwara Y, Dixon JA, Rodriguez RA, Baxter RD, Dixon DD, Collins MR, Blackmond DG, Baran PS (2012) J Am Chem Soc 134:1494–1497

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  46. Fujiwara Y, Dixon JA, O’Hara F, Funder ED, Dixon DD, Rodriguez RA, Baxter RD, Herle B, Sach N, Collins MR, Ishihara Y, Baran PS (2012) Nature 492:95–100

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  47. Gui J, Zhou Q, Pan CM, Yabe Y, Burns AC, Collins MR, Ornelas MA, Ishihara Y, Baran PS (2014) J Am Chem Soc 136:4853–4856

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  48. Li L, Mu X, Liu W, Wang Y, Mi Z, Li CJ (2016) J Am Chem Soc 138:5809–5812

    Article  CAS  PubMed  Google Scholar 

  49. Natte K, Jagadeesh RV, He L, Rabeah J, Chen J, Taeschler C, Ellinger S, Zaragoza F, Neumann H, Brückner A, Beller M (2016) Angew Chem Int Ed 55:2782–2786

    Article  CAS  Google Scholar 

  50. Jacquet J́, Blanchard S, Derat E, Murr MD, Fensterbank L (2016) Chem Sci 7:2030–2036

    Article  CAS  PubMed  Google Scholar 

  51. Katayev D, Matoušek V, Koller R, Togni A (2015) Org Lett 17:5898–5901

    Article  CAS  PubMed  Google Scholar 

  52. Sala O, Lüthi HP, Togni A, Iannuzzi M, Hutter J (2015) J Comput Chem 36:785–794

    Article  CAS  PubMed  Google Scholar 

  53. Katayev D, Václavic J, Brüning F, Commare B, Togni A (2016) Chem Commun 52:4049–4052

    Article  CAS  Google Scholar 

  54. Chen H, Li P, Wang M, Wang L (2016) Org Lett 18:4794–4797

    Article  CAS  PubMed  Google Scholar 

  55. Cuthbertson JD, MacMillan DWC (2015) Nature 519:74–77

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  56. Xiu J, Yi W (2016) Cat Sci Technol 6:998–1002

    Article  CAS  Google Scholar 

  57. Yang Q, Choy PY, Wu Y, Fan B, Kwong FY (2016) Org Biomol Chem 14:2608–2612

    Article  CAS  PubMed  Google Scholar 

  58. Mir BA, Banerjee A, Santra SK, Rajamanickam S, Patel BK (2016) Adv Synth Catal 358:3471–3476

    Article  CAS  Google Scholar 

  59. Zhao J, Fang H, Qian P, Han J, Pan Y (2014) Org Lett 16:5342–5345

    Article  CAS  PubMed  Google Scholar 

  60. Banerjee A, Santra SK, Khatun N, Ali W, Patel BK (2015) Chem Commun 51:15422–15425

    Article  CAS  Google Scholar 

  61. Wang DC, Xia R, Xie MS, Qu GR, Guo HM (2016) Org Biomol Chem 14:4189–4193

    Article  CAS  PubMed  Google Scholar 

  62. Xia R, Niu HY, Qu GR, Guo HM (2012) Org Lett 14:5546–5549

    Article  CAS  PubMed  Google Scholar 

  63. Antonchick AP, Burgmann L (2013) Angew Chem Int Ed 52:3267–3271

    Article  CAS  Google Scholar 

  64. Narayan R, Antonchick AP (2014) Chem Eur J 20:4568–4572

    Article  CAS  PubMed  Google Scholar 

  65. Liu ZQ, Li Z (2016) Chem Commun 52:14278–14281

    Article  CAS  Google Scholar 

  66. Pirnot MT, Rankic DA, Martin DBC, MacMillan DWC (2013) Science 339:1593–1596

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  67. Tang RJ, Kang L, Yang L (2015) Adv Synth Catal 357:2055–2060

    Article  CAS  Google Scholar 

  68. Paul S, Guin J (2015) Chem Eur J 21:17618–17622

    Article  CAS  PubMed  Google Scholar 

  69. Qvortrup K, Rankic DA, MacMillan DWC (2014) J Am Chem Soc 136:626–629

    Article  CAS  PubMed  Google Scholar 

  70. Jin J, MacMillan DWC (2015) Angew Chem Int Ed 54:1565–1569

    Article  CAS  Google Scholar 

  71. Ambala S, Thatikonda T, Sharma S, Munagala G, Yempalla KR, Vishwakarma RA, Singh PP (2015) Org Biomol Chem 13:11341–11350

    Article  CAS  PubMed  Google Scholar 

  72. Xie Z, Cai Y, Hu H, Lin C, Jiang J, Chen Z, Wang L, Pan Y (2013) Org Lett 15:4600–4603

    Article  CAS  PubMed  Google Scholar 

  73. He T, Yu L, Zhang L, Wang L, Wang M (2011) Org Lett 13:5016–5019

    Article  CAS  PubMed  Google Scholar 

  74. Basch CH, Liao J, Xu J, Piane JJ, Watson MP (2017) J Am Chem Soc 139:5313–5316

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  75. Prier CK, MacMillan DWC (2014) Chem Sci 5:4173–4178

    Article  CAS  PubMed  Google Scholar 

  76. Jin J, MacMillan DWC (2015) Nature 525:87–90

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  77. Bume DD, Pitts CR, Lectka T (2016) Eur J Org Chem 2016:26–30

    Google Scholar 

  78. Lu SC, Li HS, Xua S, Duan GY (2017) Org Biomol Chem 15:324–327

    Article  CAS  PubMed  Google Scholar 

  79. Neubert TD, Schmidt Y, Conroy E, Stamos D (2015) Org Lett 17:2362–2365

    Article  CAS  PubMed  Google Scholar 

  80. Correia CA, Yang L, Li CJ (2011) Org Lett 13:4581–4583

    Article  CAS  PubMed  Google Scholar 

  81. Everson DA, Shrestha R, Weix DJ (2010) J Am Chem Soc 132:920–921

    Article  CAS  PubMed  Google Scholar 

  82. Everson DA, Jones BA, Weix DJ (2012) J Am Chem Soc 134:6146–6159

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  83. Biswas S, Weix DJ (2013) J Am Chem Soc 135:16192–16197

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  84. Everson DA, Buonomo JA, Weix DJ (2014) Synlett 25:233–238

    CAS  PubMed  PubMed Central  Google Scholar 

  85. DiRocco DA, Dykstra K, Krska S, Vachal P, Conway DV, Tudge M (2014) Angew Chem Int Ed 53:4802–4806

    Article  CAS  Google Scholar 

  86. Xia R, Xie MS, Niu HY, Qu GR, Guo HM (2014) Org Lett 16:444–447

    Article  CAS  PubMed  Google Scholar 

  87. Shore DGM, Wasik KA, Lyssikatos JP, Estrada AA (2015) Tetrahedron Lett 56:4063–4066

    Article  CAS  Google Scholar 

  88. Zhao WM, Chen XL, Yuan JW, Qu LB, Duana LK, Zhao YF (2014) Chem Commun 50:2018–2020

    Article  CAS  Google Scholar 

  89. Mai DN, Baxter RD (2016) Org Lett 18:3738–3741

    Article  CAS  PubMed  Google Scholar 

  90. Hari DP, Schroll P, König B (2012) J Am Chem Soc 134:2958–2961

    Article  CAS  PubMed  Google Scholar 

  91. Zoller J, Fabry DC, Rueping M (2015) ACS Catal 5:3900–3904

    Article  CAS  Google Scholar 

  92. Zhang J, Chen J, Zhang X, Lei X (2014) J Org Chem 79:10682–10688

    Article  CAS  PubMed  Google Scholar 

  93. Xue D, Jia ZH, Zhao CJ, Zhang YY, Wang C, Xiao J (2014) Chem Eur J 2014:2960–2965

    Google Scholar 

  94. Rybicka-Jasińska K, König B, Gryko D (2017) Eur J Org Chem 2017:2104–2107

    Google Scholar 

  95. Maity P, Kundu D, Ranu BC (2015) Eur J Org Chem 2015:1727–1734

    Google Scholar 

  96. Liu YX, Xue D, Wang JD, Zhao CJ, Zou QZ, Wang C, Xiao JL (2013) Synlett 24:507–513

    Article  CAS  Google Scholar 

  97. Tobisu M, Furukawa T, Chatani N (2013) Chem Lett 42:1203–1205

    Article  CAS  Google Scholar 

  98. Natarajan P, Bala A, Mehta SK, Bhasin KK (2016) Tetrahedron 72:2521–2526

    Article  CAS  Google Scholar 

  99. Wang R, Falck RJ (2014) Org Chem Front 1:1029–1034

    Article  CAS  Google Scholar 

  100. Ghosh I, Ghosh T, Bardagi JI, König B (2014) Science 346:725–728

    Article  CAS  PubMed  Google Scholar 

  101. Ghosh I, König B (2016) Angew Chem Int Ed 55:7676–7679

    Article  CAS  Google Scholar 

  102. Arora A, Teegardin KA, Weaver JD (2015) Org Lett 17:3722–3725

    Article  CAS  PubMed  Google Scholar 

  103. Chu L, Lipshultz JM, MacMillan DWC (2015) Angew Chem Int Ed 54:7929–7933

    Article  CAS  Google Scholar 

  104. Cheng WM, Shang R, Yu HZ, Fu Y (2015) Chem Eur J 21:13191–13195

    Article  CAS  PubMed  Google Scholar 

  105. Shi Q, Li P, Zhu X, Wang L (2016) Green Chem 18:4916–4923

    Article  CAS  Google Scholar 

  106. Sharma UK, Gemoets HPL, Schröder F, Noël T, Van der Eycken EV (2017) ACS Catal 7:3818–3823

    Article  CAS  Google Scholar 

  107. Gu L, Jin C, Liu J, Zhang H, Yuan M, Li G (2016) Green Chem 18:1201–1205

    Article  CAS  Google Scholar 

  108. Cheng P, Qing Z, Liu S, Liu W, Xie H, Zeng J (2014) Tetrahedron Lett 55:6647–6651

    Article  CAS  Google Scholar 

  109. Matcha K, Antonchick AP (2013) Angew Chem Int Ed 52:2082–2086

    Article  CAS  Google Scholar 

  110. Siddaraju Y, Lamani M, Prabhu KR (2014) J Org Chem 79:3856–3865

    Article  CAS  PubMed  Google Scholar 

  111. Siddaraju Y, Prabhu KR (2016) Tetrahedron 72:959–967

    Article  CAS  Google Scholar 

  112. Chen J, Wan M, Hua J, Sun Y, Lv Z, Li W, Liu L (2015) Org Biomol Chem 13:11561–11566

    Article  CAS  PubMed  Google Scholar 

  113. Ali W, Behera A, Guin S, Patel BK (2015) J Org Chem 80:5625–5632

    Article  CAS  PubMed  Google Scholar 

  114. Wan M, Lou H, Liu L (2015) Chem Commun 51:13953–13956

    Article  CAS  Google Scholar 

  115. Suresh R, Kumaran RS, Senthilkumar V, Muthusubramanian S (2014) RSC Adv 4:31685–31688

    Article  CAS  Google Scholar 

  116. Laha JK, Patel KV, Dubey G, Jethava KP (2017) Org Biomol Chem 15:2199–2210

    Article  CAS  PubMed  Google Scholar 

  117. Lo JC, Gui J, Yabe Y, Pan CM, Baran PS (2014) Nature 516:343–348

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  118. Lo JC, Kim D, Pan CM, Edwards JT, Yabe Y, Gui J, Qin T, Gutiérrez S, Giacoboni J, Smith MW, Holland PL, Baran PS (2017) J Am Chem Soc 139:2484–2503

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  119. Crossley SWM, Martinez RM, Guevara-Zuluaga S, Shenvi RA (2016) Org Lett 18:2620–2623

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  120. Ma X, Herzon SB (2016) J Am Chem Soc 138:8718–8721

    Article  CAS  PubMed  Google Scholar 

  121. Ma X, Dang H, Rose JA, Rablen P, Herzon SB (2017) J Am Chem Soc 139:5998–6007

    Article  CAS  PubMed  Google Scholar 

  122. Green SA, Matos JLM, Yagi A, Shenvi RA (2016) J Am Chem Soc 138:12779–12782

    Article  CAS  PubMed  Google Scholar 

  123. Foo K, Sella E, Thomé I, Eastgate MD, Baran PS (2014) J Am Chem Soc 136:5279–5282

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  124. Davies J, Svejstrup TD, Reina DF, Sheikh NS, Leonori D (2016) J Am Chem Soc 138:8092–8095

    Article  CAS  PubMed  Google Scholar 

  125. Li M, Petersen JL, Hoover JM (2017) Org Lett 19:638–641

    Article  CAS  PubMed  Google Scholar 

  126. Li L, Liu W, Zeng H, Mu X, Cosa G, Mi Z, Li CJ (2015) J Am Chem Soc 137:8328–8331

    Article  CAS  PubMed  Google Scholar 

  127. Li L, Liu W, Mu X, Mi Z, Li CJ (2016) Nat Protoc 11:1948–1954

    Article  CAS  PubMed  Google Scholar 

  128. Dutta U, Deb A, Lupton DW, Maiti D (2015) Chem Commun 51:17744–17747

    Article  CAS  Google Scholar 

  129. Sharma KK, Patel DI, Jain R (2015) Chem Commun 51:15129–15132

    Article  CAS  Google Scholar 

  130. Mondal M, Bora U (2013) RSC Adv 3:18716–18754

    Article  CAS  Google Scholar 

  131. Berger O, Montchamp JL (2014) Chem Eur J 20:12385–12388

    Article  CAS  PubMed  Google Scholar 

  132. Li L, Wang JJ, Wang GW (2016) J Org Chem 81:5433–5439

    Article  CAS  PubMed  Google Scholar 

  133. Li Zhang L, Jiao L (2017) J Am Chem Soc 139:607–610

    Article  PubMed  CAS  Google Scholar 

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Author information

Authors and Affiliations

  1. Department of Chemical Biology, Max-Planck Institute for Molecular Physiology, Otto-Hahn Straße 11, Dortmund, 44227, Germany

    Jomy Joseph & Andrey P. Antonchick

  2. Department of Chemistry and Chemical Biology, Technische Universität Dortmund, Otto-Hahn Straße 4a, Dortmund, 44227, Germany

    Andrey P. Antonchick

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  1. Jomy Joseph
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Correspondence to Andrey P. Antonchick .

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Editors and Affiliations

  1. University of Bordeaux, Talence, France

    Yannick Landais

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Joseph, J., Antonchick, A.P. (2017). Free Radicals in Heterocycle Functionalization. In: Landais, Y. (eds) Free-Radical Synthesis and Functionalization of Heterocycles. Topics in Heterocyclic Chemistry, vol 54. Springer, Cham. https://doi.org/10.1007/7081_2017_8

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