Citation: ZHAO Mengdi, LU Wenjun. Alkanes Functionalization via C-H Activation[J]. Acta Physico-Chimica Sinica, ;2019, 35(9): 977-988. doi: 10.3866/PKU.WHXB201811045 shu

Alkanes Functionalization via C-H Activation

ZHAO Mengdi ,
LU Wenjun ^,

Department of Chemistry, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Corresponding author: LU Wenjun, luwj@sjtu.edu.cn
Received Date: 30 November 2018
Revised Date: 11 January 2019
Accepted Date: 15 January 2019
Available Online: 18 September 2019
Fund Project: The project supported by the National Natural Science Foundation of China (21372153)the National Natural Science Foundation of China 21372153

Normal alkyl sp³C―H bonds are ubiquitous in compounds such as methane, linear alkanes, and cycloalkanes that are not linked directly to heteroatoms or other functional groups. These unactivated bonds are not broken readily under mild conditions because their bond dissociation energy values are high and acidity values are low. Moreover, in the radical processes at high temperatures, reaction selectivity is not good for an alkane substrate with various alkyl sp³C―H bonds, which is commonly methyl < 1° < 2° < 3°. In the past five decades, C―H activation by transition-metal species to give C-metal bonds under mild conditions was intensively studied; all efforts were undertaken to provide new methods that can be applied in both chemical synthesis and chemical industry. However, the effective transformations of inert C―H bonds, particularly alkyl sp³C―H bonds, without the assistance of directing groups have been rarely investigated. This review focuses on the functionalization of normal alkyl sp³C―H bonds, such as methyl and primary sp³C―H bonds, via electrophilic activation or oxidative addition by using homogenous transition-metal catalysts, which are two main strategies in the study of inert C―H activation. The selectivity on C―H bond is methyl > 1° > 2° > 3° in both the reactions. Neither heterogeneous catalysis nor biocatalysis is mentioned in this review. Some remarkable progress is described on the study of reaction mechanisms and the establishment of novel reactions. For example, several selective oxidations of methane or linear alkanes have been introduced to afford new C―O, C―Cl, or even C―C bonds in the presence of Pt or Pd catalysts. The Shilov chemistry, which combines electrophilic activation of the C―H bond by the transition-metal complex, oxidation of the transition-metal intermediate, and nucleophilic substitution of organometallic species, has been emphasized in these reactions. Other transition-metal catalysts including Rh, Ir, Re, and W have been employed successfully in the carbonylation, borylation, and dehydrogenation of alkanes at moderate temperatures. The reaction pathways normally involve oxidative addition of the C―H bond with the transition-metal complex followed by insertion-elimination, reductive elimination, or β-H elimination. In the cascade reactions consisting of dehydrogenation of alkanes and addition of alkenes, new C―C or C―Si bonds can also be formed at terminal sites of linear alkanes. However, most of the above-mentioned reactions are still under investigation because of limited scope of the substrate, excess loading of the alkane, low efficiency of the catalyst, and high cost of the reaction operation. Breakthroughs in this promising field of alkane functionalization are possible when new concepts and technology are realized and applied.
- Alkane,
- C―H activation,
- Functionalization,
- Selectivity,
- Transition metal
1. [1]
  Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. doi: 10.1021/ar00051a009 doi: 10.1021/ar00051a009
2. [2]
  Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879. doi: 10.1021/cr9411886 doi: 10.1021/cr9411886
3. [3]
  Jia, C.; Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633. doi: 10.1021/ar000209h doi: 10.1021/ar000209h
4. [4]
  Crabtree, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437. doi: 10.1039/b103147n doi: 10.1039/b103147n
5. [5]
  Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. doi: 10.1038/417507a doi: 10.1038/417507a
6. [6]
  Lu, W.; Zhou, L. Oxidation of C‒H Bonds; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2017.
7. [7]
  Luo, Y. -R. Comprehensive Handbook of Chemical Bond Energies; CRC Press.: Boca Raton, FL, USA, 2007.
8. [8]
  Egloff, G.; Schaad, R. E.; Lowry, C. D., Jr. Chem. Rev. 1931, 8, 1. doi: 10.1021/cr60029a001 doi: 10.1021/cr60029a001
9. [9]
  Lin, R.; Amrute, A. P.; Pérez-Ramírez, J. Chem. Rev. 2017, 117, 4182. doi: 10.1021/acs.chemrev.6b00551 doi: 10.1021/acs.chemrev.6b00551
10. [10]
  Zhao, M.; Lu, W. Org. Lett. 2017, 19, 4560. doi: 10.1021/acs.orglett.7b02153 doi: 10.1021/acs.orglett.7b02153
11. [11]
  Zhao, M.; Lu, W. Org. Lett. 2018, 20, 5264. doi: 10.1021/acs.orglett.8b02208 doi: 10.1021/acs.orglett.8b02208
12. [12]
  Olah, G. A. Acc. Chem. Res. 1987, 20, 422. doi: 10.1021/ar00143a006 doi: 10.1021/ar00143a006
13. [13]
  Olah, G. A. Angew. Chem. Int. Edit. 1995, 34, 1393. doi: 10.1002/anie.199513931 doi: 10.1002/anie.199513931
14. [14]
  Olah, G. A.; Klumpp, D. A. Superelectrophiles and Their Chemistry; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2008.
15. [15]
  Zhou, L.; Lu, W. Acta Chim. Sin. 2015, 73, 1250.[ doi: 10.6023/A15040278
16. [16]
  Zhou, L.; Lu, W. Org. Lett. 2014, 16, 508. doi: 10.1021/ol403393w doi: 10.1021/ol403393w
17. [17]
  Zhao, R.; Lu, W. Org. Lett. 2017, 19, 1768. doi: 10.1021/acs.orglett.7b00536 doi: 10.1021/acs.orglett.7b00536
18. [18]
  Zhao, R.; Lu, W. Organometallics 2018, 37, 2188. doi: 10.1021/acs.organomet.8b00325 doi: 10.1021/acs.organomet.8b00325
19. [19]
  Labinger, J. A.; Bercaw, J. E. J. Organomet. Chem. 2015, 793, 47. doi: 10.1016/j.jorganchem.2015.01.027 doi: 10.1016/j.jorganchem.2015.01.027
20. [20]
  Garnett, J. L.; Hodges, R. J. J. Am. Chem. Soc. 1967, 89, 4546. doi: 10.1021/ja00993a067 doi: 10.1021/ja00993a067
21. [21]
  Labinger, J. A.; Herring, A. M.; Bercaw, J. E. J. Am. Chem. Soc. 1990, 112, 5628. doi: 10.1021/ja00170a031 doi: 10.1021/ja00170a031
22. [22]
  Sen, A.; Benvenuto, M. A.; Lin, M.; Hutson, A. C. Basickes, N. J. Am. Chem. Soc. 1994, 116, 998. doi: 10.1021/ja00082a022 doi: 10.1021/ja00082a022
23. [23]
  Dangel, B. D.; Johnson, J. A.; Sames, D. J. Am. Chem. Soc. 2001, 123, 8149. doi: 10.1021/ja016280f doi: 10.1021/ja016280f
24. [24]
  Weinberg, D. R.; Labinger, J. A.; Bercaw, J. E. Organometallics 2007, 26, 167. doi: 10.1021/om060763g doi: 10.1021/om060763g
25. [25]
  Lee, M.; Sanford, M. S. J. Am. Chem. Soc. 2015, 137, 12796 and references therein. doi: 10.1021/jacs.5b09099 doi: 10.1021/jacs.5b09099
26. [26]
  Periana, R. A.; Taube, D. J.; Evitt, E. R.; L ffler, D. G.; Wentrcek, P. R.; Voss, G.; Masuda, T. Science 1993, 259, 340. doi: 10.1126/science.259.5093.340 doi: 10.1126/science.259.5093.340
27. [27]
  Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science 1998, 280, 560. doi: 10.1126/science.280.5363.560 doi: 10.1126/science.280.5363.560
28. [28]
  Gunsalus, N. J.; Konnick, M. M.; Hashiguchi, B. G.; Periana, R. A. Isr. J. Chem. 2014, 54, 1467. doi: 10.1002/ijch.201300130 doi: 10.1002/ijch.201300130
29. [29]
  Gunsalus, N. J.; Koppaka, A.; Park, S. H.; Bischof, S. M.; Hashiguchi, B. G.; Periana, R. A. Chem. Rev. 2017, 117, 8521. doi: 10.1021/acs.chemrev.6b00739 doi: 10.1021/acs.chemrev.6b00739
30. [30]
  Curto, J. M.; Kozlowski, M. C. J. Am. Chem. Soc. 2015, 137, 18. doi: 10.1021/ja5093166 doi: 10.1021/ja5093166
31. [31]
  Sakakura, T.; Tanaka, M. J. Chem. Soc. Chem. Commun. 1987, 758. doi: 10.1039/C39870000758 doi: 10.1039/C39870000758
32. [32]
  Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J. Am. Chem. Soc. 1990, 112, 7221. doi: 10.1021/ja00176a022 doi: 10.1021/ja00176a022
33. [33]
  Lin, M.; Sen, A. Nature 1994, 368, 613. doi: 10.1038/368613a0 doi: 10.1038/368613a0
34. [34]
  Waltz, K. M.; Hartwig, J. F. Science 1997, 277, 211. doi: 10.1126/science.277.5323.211 doi: 10.1126/science.277.5323.211
35. [35]
  Chen, H.; Hartwig, J. F. Angew. Chem. Int. Edit. 1999, 38, 3391. doi: 10.1002/(SICI)1521-3773(19991115)38:22<3391::AID-ANIE3391 > 3.0.CO; 2-N doi: 10.1002/(SICI)1521-3773(19991115)38:22<3391::AID-ANIE3391>3.0.CO;2-N
36. [36]
  Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287, 1995. doi: 10.1126/science.287.5460.1995 doi: 10.1126/science.287.5460.1995
37. [37]
  Cook, A. K.; Schimler, S. D.; Matzger, A. J.; Sanford, M. S. Science 2016, 351, 1421. doi: 10.1126/science.aad9289 doi: 10.1126/science.aad9289
38. [38]
  Smith, K. T.; Berritt, S.; González-Moreiras, M.; Ahn, S.; Smith, M. R., Ⅲ; Baik, M. -H.; Mindiola, D. J. Science 2016, 351, 1424. doi: 10.1126/science.aad9730 doi: 10.1126/science.aad9730
39. [39]
  Crabtree, R. H.; Mihelcic, J. M.; Quirk, J. M. J. Am. Chem. Soc. 1979, 101, 7738. doi: 10.1021/ja00520a030 doi: 10.1021/ja00520a030
40. [40]
  Baudry, D.; Ephritikhine, M.; Felkin, H.; Holmes-Smith, R. J. Chem. Soc. Chem. Commun. 1983, 788. doi: 10.1039/C39830000788 doi: 10.1039/C39830000788
41. [41]
  Burk, M. J.; Crabtree, R. H.; McGrath, D. V. J. Chem. Soc. Chem. Commun. 1985, 1829. doi: 10.1039/C39850001829 doi: 10.1039/C39850001829
42. [42]
  Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025. doi: 10.1021/ja00260a013 doi: 10.1021/ja00260a013
43. [43]
  Fujii, T.; Saito, Y. J. Chem. Soc. Chem. Commun. 1990, 757. doi: 10.1039/C39900000757 doi: 10.1039/C39900000757
44. [44]
  Aoki, T.; Crabtree, R. H. Organometallics 1993, 12, 294. doi: 10.1021/om00026a013 doi: 10.1021/om00026a013
45. [45]
  Liu, F.; Pak, E. B.; Singh, B.; Jensen, C. M.; Goldman, A. S. J. Am. Chem. Soc. 1999, 121, 4086. doi: 10.1021/ja983460p doi: 10.1021/ja983460p
46. [46]
  Dobereiner, G. E.; Crabtree, R. H. Chem. Rev. 2010, 110, 681. doi: 10.1021/cr900202j doi: 10.1021/cr900202j
47. [47]
  Kumar, A.; Bhatti, T. M.; Goldman, A. S. Chem. Rev. 2017, 117, 12357. doi: 10.1021/acs.chemrev.7b00247 doi: 10.1021/acs.chemrev.7b00247
48. [48]
  Chowdhury, A. D.; Weding, N.; Julis, J.; Franke, R.; Jackstell, R.; Beller, M. Angew. Chem. Int. Edit. 2014, 53, 6477. doi: 10.1002/anie.201402287 doi: 10.1002/anie.201402287
49. [49]
  Sommer, H.; Juliá-Hernández, F.; Martin, R.; Marek, I. ACS Cent. Sci. 2018, 4, 153. doi: 10.1021/acscentsci.8b00005 doi: 10.1021/acscentsci.8b00005
50. [50]
  van Leeuwen, P. W. N. M.; Kamer, P. C.; Reek, J. N. H.; Dierkes, P. Chem. Rev. 2000, 100, 2741. doi: 10.1021/cr9902704 doi: 10.1021/cr9902704
51. [51]
  Seayad, A.; Ahmed, M.; Klein, H.; Jackstell, R.; Gross, T.; Beller, M. Science 2002, 297, 1676. doi: 10.1126/science.1074801 doi: 10.1126/science.1074801
52. [52]
  Tang, X. Jia, X.; Huang, Z. J. Am. Chem. Soc. 2018, 140, 4157. doi: 10.1021/jacs.8b01526 doi: 10.1021/jacs.8b01526
53. [53]
  Goldman, A. S.; Roy, A. H.; Huang, Z.; Ahuja, R.; Schinski, W.; Brookhart, M. Science 2006, 312, 257. doi: 10.1126/science.1123787 doi: 10.1126/science.1123787
54. [54]
  Dupuy, S.; Zhang, K. -F.; Goutierre, A. -S.; Baudoin, O. Angew. Chem. Int. Edit. 2016, 55, 14793. doi: 10.1002/anie.201608535 doi: 10.1002/anie.201608535
55. [55]
  Juliá-Hernández, F.; Moragas, T.; Cornella, J.; Martin, R. Nature 2017, 545, 84. doi: 10.1038/nature22316 doi: 10.1038/nature22316
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