Catalysis Letters

, Volume 145, Issue 1, pp 458–467 | Cite as

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation



The past two decades have witnessed explosive growth in the field of catalytic C–H activation. While this reactivity is typically associated with second- and third-row transition metals, first-row transition metals are also capable of catalyzing these reactions. C–H activation reactions can be further divided into ones where the C–H activation occurs with a low-valent metal and those where the activation occurs with a high-valent metal. This review will summarize advances in the area of high-valent Co(III)- and Ni(II)-catalyzed C–H activation with particular emphasis paid to how these catalysts compare their second- and third-row congeners.

Graphical abstract


Catalysis C–H bond activation C–C coupling Homogeneous catalysis 



I thank Derek M. Dalton, Erin E. Stache, Kerem E. Ozboya, Kyle E. Ruhl, and John A. McIntosh for helpful comments on the manuscript.


  1. 1.
    Chen X, Engle KM, Wang DH, Yu JQ (2009) Angew Chem Int Ed 48:5094CrossRefGoogle Scholar
  2. 2.
    Colby DA, Bergman RG, Ellman JA (2010) Chem Rev 110:624CrossRefGoogle Scholar
  3. 3.
    Lyons TW, Sanford MS (2010) Chem Rev 110:1147CrossRefGoogle Scholar
  4. 4.
    Wencel-Delord J, Dröge T, Liu F, Glorius F (2011) Chem Soc Rev 40:4740CrossRefGoogle Scholar
  5. 5.
    Davies HML, Du Bois J, Yu JQ (2011) Chem Soc Rev 40:1855CrossRefGoogle Scholar
  6. 6.
    Patureau FW, Wencel-Delord J, Glorius F (2012) Aldrichimica Acta 45:31Google Scholar
  7. 7.
    Engle KM, Yu JQ (2013) J Org Chem 78:8927CrossRefGoogle Scholar
  8. 8.
    Hartwig JF (2011) Chem Soc Rev 40:1992CrossRefGoogle Scholar
  9. 9.
    Seechurn CCCJ, Kitching MO, Colacot TJ, Sniekus V (2012) Angew Chem Int Ed 51:5062CrossRefGoogle Scholar
  10. 10.
    Enghag P (2004) Encyclopedia of elements. Wiley, WeinheimCrossRefGoogle Scholar
  11. 11.
    Czaplik WM, Mayer M, Cvengros J, von Wangelin AJ (2009) ChemSusChem 2:396CrossRefGoogle Scholar
  12. 12.
    Bolm C, Legros J, Le Paih J, Zani L (2004) Chem Rev 104:6217CrossRefGoogle Scholar
  13. 13.
    Enthaler S, Junge K, Beller M (2008) Angew Chem Int Ed 47:3317CrossRefGoogle Scholar
  14. 14.
    Kulkarni AA, Daugulis O (2009) Synthesis 24:4087Google Scholar
  15. 15.
    Gosmini C, Bégouin JM, Moncombie A (2008) Chem Commun 3221:33Google Scholar
  16. 16.
    Cahiez G, Moyeux A (2010) Chem Rev 110:1435CrossRefGoogle Scholar
  17. 17.
    Rosen B, Quasdorf KW, Wilson DA, Zhang N, Resmerita AM, Garg NK, Percec V (2011) Chem Rev 111:1346CrossRefGoogle Scholar
  18. 18.
    Jana R, Pathak TP, Sigman MS (2011) Chem Rev 111:1417CrossRefGoogle Scholar
  19. 19.
    Tasker SZ, Standley EA, Jamison TF (2014) Nature 509:299CrossRefGoogle Scholar
  20. 20.
    Shopta H, Ano Y, Aihara Y, Fukumoto Y, Chatani N (2011) J Am Chem Soc 133:14952CrossRefGoogle Scholar
  21. 21.
    Kleiman JP, Dubeck MJ (1963) J Am Chem Soc 85:1544CrossRefGoogle Scholar
  22. 22.
    Gao K, Yoshikai N (2014) Acc Chem Res 47:1208CrossRefGoogle Scholar
  23. 23.
    Sun CL, Li BJ, Shi ZJ (2011) Chem Rev 111:1293CrossRefGoogle Scholar
  24. 24.
    Nakamura E, Yoshikai N (2010) J Org Chem 75:6061CrossRefGoogle Scholar
  25. 25.
    Wendlandt AE, Suess AM, Stahl SS (2011) Angew Chem Int Ed 50:11062CrossRefGoogle Scholar
  26. 26.
    Gao K, Lee PS, Fujita T, Yoshikai N (2010) J Am Chem Soc 132:12249CrossRefGoogle Scholar
  27. 27.
    Colby DA, Tsai AS, Bergman RG, Ellman JA (2012) Acc Chem Res 45:814CrossRefGoogle Scholar
  28. 28.
    Lenges CP, Brookhart M (1999) J Am Chem Soc 121:6616CrossRefGoogle Scholar
  29. 29.
    Zhang YJ, Skucas E, Krische MJ (2009) Org Lett 11:4248CrossRefGoogle Scholar
  30. 30.
    Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N (1993) Nature 366:529CrossRefGoogle Scholar
  31. 31.
    Lapointe D, Fagnou K (2010) Chem Lett 39:1118CrossRefGoogle Scholar
  32. 32.
    Davies DL, Donald SMA, Al-Duaij O, Macgregor SA, Pölleth M (2006) J Am Chem Soc 128:4210CrossRefGoogle Scholar
  33. 33.
    Boutadla Y, Davies DL, Macgregor SA, Poblador-Bahamonde AI (2009) Dalton Trans 38:5887CrossRefGoogle Scholar
  34. 34.
    Zhang Q, Yu HZ, Li YT, Liu L, Huang Y, Fu Y (2013) Dalton Trans 42:4175CrossRefGoogle Scholar
  35. 35.
    Davies DL, Donald SMA, Macgregor SA (2005) J Am Chem Soc 127:13754CrossRefGoogle Scholar
  36. 36.
    Miura M, Satoh T (2010) Chem Eur J 16:11212CrossRefGoogle Scholar
  37. 37.
    Song G, Wang F, Li X (2012) Chem Soc Rev 41:3651CrossRefGoogle Scholar
  38. 38.
    Patureau FW, Wencel-Delord J, Glorius F (2012) Aldrichemica Acta 45:31Google Scholar
  39. 39.
    Zhu C, Wang R, Falck JR (2012) Chem Asian J 7:1502CrossRefGoogle Scholar
  40. 40.
    Yoshino T, Ikemoto H, Matsunaga S, Kanai M (2013) Angew Chem Int Ed 52:2207CrossRefGoogle Scholar
  41. 41.
    Tsia AS, Tauchert ME, Bergman RG, Ellman JA (2011) J Am Chem Soc 133:1248CrossRefGoogle Scholar
  42. 42.
    Tauchert ME, Incarvito CD, Rheingold AL, Bergman RG, Ellman JA (2012) Angew Chem Int Ed 134:1482Google Scholar
  43. 43.
    Li Y, Zhang XS, Li H, Wang WH, Chen K, Li BJ, Shi ZJ (2012) Chem Sci 3:1634CrossRefGoogle Scholar
  44. 44.
    Gao K, Yoshikai N (2012) Chem Commun 48:4305CrossRefGoogle Scholar
  45. 45.
    Sun B, Yoshino T, Matsunaga S, Kanai M (2014) Adv Synth Catal 356:1491CrossRefGoogle Scholar
  46. 46.
    Kim JK, Park SH, Ryu J, Cho SH, Kim SH, Chang S (2012) J Am Chem Soc 134:9110CrossRefGoogle Scholar
  47. 47.
    Lee D, Kim Y, Chang S (2013) J Org Chem 78:11102CrossRefGoogle Scholar
  48. 48.
    Park SH, Kwak J, Shin K, Ryu J, Park Y, Chang S (2014) J Am Chem Soc 136:2492CrossRefGoogle Scholar
  49. 49.
    Ikemoto H, Yoshino T, Sakata K, Matsunaga S, Kanai M (2014) J Am Chem Soc 136:5424CrossRefGoogle Scholar
  50. 50.
    Schipper DJ, Hutchinson M, Fagnou K (2010) J Am Chem Soc 132:6910CrossRefGoogle Scholar
  51. 51.
    Guimond N, Gorelsky SI, Fagnou K (2011) J Am Chem Soc 133:6449CrossRefGoogle Scholar
  52. 52.
    Wang H, Grohmann C, Nimphius C, Glorius F (2012) J Am Chem Soc 134:19592CrossRefGoogle Scholar
  53. 53.
    Li BJ, Wang HY, Zhu QL, Shi ZJ (2012) Angew Chem Int Ed 51:3948CrossRefGoogle Scholar
  54. 54.
    Grigorjeva L, Daugulis O (2014) Angew Chem Int Ed 53:10209CrossRefGoogle Scholar
  55. 55.
    Guimond N, Gouliaras C, Fagnou K (2010) J Am Chem Soc 132:6908CrossRefGoogle Scholar
  56. 56.
    Mochida S, Umeda N, Hirano K, Satoh T, Miura M (2010) Chem Lett 39:744CrossRefGoogle Scholar
  57. 57.
    Hyster TK, Rovis T (2010) J Am Chem Soc 132:10565CrossRefGoogle Scholar
  58. 58.
    Song G, Chen D, Pan CL, Crabtree RH, Li X (2010) J Org Chem 75:7487CrossRefGoogle Scholar
  59. 59.
    Zaitsev VG, Shabashov D, Daugulis O (2005) J Am Chem Soc 127:13154CrossRefGoogle Scholar
  60. 60.
    Shabashov D, Daugulis O (2010) J Am Chem Soc 132:3965CrossRefGoogle Scholar
  61. 61.
    Stuart DR, Bertrand-Laperle M, Burgess KMN, Fagnou K (2008) J Am Chem Soc 130:16474CrossRefGoogle Scholar
  62. 62.
    Guimond N, Fagnou K (2009) J Am Chem Soc 131:12050CrossRefGoogle Scholar
  63. 63.
    Ackermann L, Lygin AV, Hofmann N (2011) Angew Chem Int Ed 50:6379CrossRefGoogle Scholar
  64. 64.
    Guimond N, Gorelsky SI, Fagnou K (2011) J Am Chem Soc 133:6449CrossRefGoogle Scholar
  65. 65.
    Grigorjeva L, Daugulis O (2014) Org Lett 16:4688CrossRefGoogle Scholar
  66. 66.
    Grigorjeva L, Daugulis O (2014) Org Lett 16:4684CrossRefGoogle Scholar
  67. 67.
    Rakshit S, Grohmann C, Besset T, Glorius F (2011) J Am Chem Soc 133:2350CrossRefGoogle Scholar
  68. 68.
    Hyster TK, Dalton DM, Rovis T (2014) Chem Sci. doi: 10.1039/c4sc02590c Google Scholar
  69. 69.
    Canivet J, Yamaguchi J, Ban I, Itami K (2009) Org Lett 11:1733CrossRefGoogle Scholar
  70. 70.
    Muto K, Yamaguchi J, Itami K (2012) J Am Chem Soc 134:169CrossRefGoogle Scholar
  71. 71.
    Pivsa-Art S, Satoh T, Kawamura Y, Miura M, Nomura M (1998) Bull Chem Soc Jpn 71:467CrossRefGoogle Scholar
  72. 72.
    Campeau LC, Parisien M, Leblanc M, Fagnou K (2004) J Am Chem Soc 126:9186CrossRefGoogle Scholar
  73. 73.
    Ames DE, Opalko A (1984) Tetrahedron 40:1919CrossRefGoogle Scholar
  74. 74.
    Wang J, Ferguson DM, Kalyani D (2013) Tetrahedron 69:5780CrossRefGoogle Scholar
  75. 75.
    Muto K, Yamaguchi J, Lei A, Itami K (2013) J Am Chem Soc 135:16384CrossRefGoogle Scholar
  76. 76.
    Bellina F, Rossi R (2010) Chem Rev 110:1082CrossRefGoogle Scholar
  77. 77.
    Burtoloso ACB (2009) Synlett 320Google Scholar
  78. 78.
    Culkin DA, Hartwig JF (2003) Acc Chem Res 36:234CrossRefGoogle Scholar
  79. 79.
    Lloyd-Jones GC (2002) Angew Chem Int Ed 41:953CrossRefGoogle Scholar
  80. 80.
    Takise R, Muto K, Yamaguchi J, Itami K (2014) Angew Chem Int Ed 53:6791CrossRefGoogle Scholar
  81. 81.
    Amaike K, Muta K, Yamaguchi J, Itami K (2012) J Am Chem Soc 134:13573CrossRefGoogle Scholar
  82. 82.
    Meng L, Kamada Y, Muto K, Yamaguchi J, Itami K (2013) Angew Chem Int Ed 52:10048CrossRefGoogle Scholar
  83. 83.
    Hong X, Liang Y, Houk KN (2014) J Am Chem Soc 136:2017CrossRefGoogle Scholar
  84. 84.
    Lu Q, Yu H, Fu Y (2014) J Am Chem Soc 136:8252CrossRefGoogle Scholar
  85. 85.
    Zhao X, Yu Z (2008) J Am Chem Soc 130:8136CrossRefGoogle Scholar
  86. 86.
    Jin W, Yu Z, He W, Ye W, Xiao WJ (2009) Org Lett 11:1317CrossRefGoogle Scholar
  87. 87.
    Aihara Y, Chatani N (2013) J Am Chem Soc 135:5308CrossRefGoogle Scholar
  88. 88.
    Song W, Lackner S, Ackermann L (2014) Angew Chem Int Ed 53:2477CrossRefGoogle Scholar
  89. 89.
    Cong X, Li Y, Wei Y, Zeng X (2014) Org Lett 16:3926CrossRefGoogle Scholar
  90. 90.
    Yokota A, Aihara Y, Chatani N (2014) J Org Chem. doi: 10.1021/jo501697n Google Scholar
  91. 91.
    Aihara Y, Chatani N (2014) J Am Chem Soc 136:898CrossRefGoogle Scholar
  92. 92.
    Li M, Dong J, Huang X, Li K, Wu Q, Song F, You J (2014) Chem Commun 50:3944CrossRefGoogle Scholar
  93. 93.
    Nadres ET, Santos GIF, Shabashov D, Daugulis O (2013) J Org Chem 78:9689CrossRefGoogle Scholar
  94. 94.
    Zhang SY, Li Q, He G, Nack WA, Chen G (2013) J Am Chem Soc 135:12135CrossRefGoogle Scholar
  95. 95.
    Wu X, Zhao Y, Ge H (2014) J Am Chem Soc 136:1789CrossRefGoogle Scholar
  96. 96.
    Wu X, Zhao Y, Ge H (2014) Chem Eur J 20:9530CrossRefGoogle Scholar
  97. 97.
    He G, Zhang SY, Nack WA, Li Q, Chen G (2013) Angew Chem Int Ed 52:11124CrossRefGoogle Scholar
  98. 98.
    Nadres ET, Daugulis O (2012) J Am Chem Soc 134:7CrossRefGoogle Scholar
  99. 99.
    Yoshida Y, Kurahashi T, Matsubara S (2011) Chem Lett 40:1140CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  1. 1.Department of Chemistry and Chemical EngineeringCalifornia Institute of TechnologyPasadenaUSA

Personalised recommendations