Citation: Huang Jiapian, Gu Qing, You Shuli. Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C-H Bond Functionalization[J]. Chinese Journal of Organic Chemistry, ;2018, 38(1): 51-61. doi: 10.6023/cjoc201708030 shu

Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C-H Bond Functionalization

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Gu Qing, qinggu@sioc.ac.cn You Shuli, slyou@sioc.ac.cn
Received Date: 15 August 2017
Revised Date: 13 September 2017
Available Online: 15 January 2017
Fund Project: the National Natural Science Foundation of China 21572250Project supported by the National Key R&D Program of China (No. 2016YFA0202900), the National Basic Research Program of China (973 Program, No. 2015CB856600), the National Natural Science Foundation of China (Nos. 21332009, 21421091, 21572250), and the Chinese Academy Sciences (Nos. XDB20000000, QYZDY-SSW-SLH012)the National Basic Research Program of China 2015CB856600the Chinese Academy Sciences XDB20000000the National Key R&D Program of China 2016YFA0202900the Chinese Academy Sciences QYZDY-SSW-SLH012the National Basic Research Program of China 973 Programthe National Natural Science Foundation of China 21421091the National Natural Science Foundation of China 21332009

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Ferrocenes bearing planar chirality have been demonstrated to be highly efficient ligands or catalysts in asymmetric catalysis. In view of their atom and step economies, direct asymmetric C—H bond functionalization is the most concise and powerful method for the construction of planar chiral ferrocenes compared with traditional approaches. This review summarizes recent progress on the development of novel methods to synthesize planar chiral compounds via transition-metal (Cu-, Pd-, Ir-, Rh-, Au-, Pt-) catalyzed asymmetric C—H bond functionalization. Preparation of a variety of new planar chiral ferrocene-based catalysts and ligands by utilizing these methods and their application in catalytic asymmetric reactions are also discussed.
- transition metal catalysis,
- asymmetric catalysis,
- direct C-H bond functionalization,
- planar chirality,
- ferrocene
1. [1]
  (a) Hayashi, T.; Togni, A. Ferrocenes, VCH, Weinheim, Germany, 1995.
  (b) Togni, A.; Haltermann, R. L. Metallocenes, VCH, Weinheim, Germany, 1998.
  (c) Štěpnička, P. Ferrocenes, Wiley, Chichester, 2008.
  (d) Dai, L.-X.; Hou, X.-L. Chiral Ferrocenes in Asymmetric Catalysis, Wiley, Weinheim, 2010.
2. [2]
3. [3]
  (a) Blaser, H.-U.; Brieden, W.; Pugin, B.; Spindler, F.; Studer, M.; Togni, A. Top. Catal. 2002, 19, 3.
  (b) Blaser, H.-U.; Pugin, B.; Spindler, F. J. Mol. Catal. A 2005, 231, 1.
4. [4]
  (a) Battelle, L. F.; Bau, R.; Gokel, G. W.; Oyakawa, R. T.; Ugi, I. K. J. Am. Chem. Soc. 1973, 95, 482.
  (b) Rebière, F.; Riant, O.; Ricard, L.; Kagan, H. B. Angew. Chem., Int. Ed. 1993, 32, 568.
  (c) Richards, C. J.; Damalidis, T.; Hibbs, D. E.; Hursthouse, M. B. Synlett 1995, 74.
  (d) Tsukazaki, M.; Tinkl, M.; Roglans, A.; Chapell, B. J.; Taylor, N. J.; Snieckus, V. J. Am. Chem. Soc. 1996, 118, 685.
  (e) Enders, D.; Peters, R.; Lochtman, R.; Raabe, G. Angew. Chem., Int. Ed. 1999, 38, 2421.
  (f) Laufer, R. S.; Veith, U.; Taylor, N. J.; Snieckus, V. Org. Lett. 2000, 2, 629.
  (g) Bolm, C.; Kesselgruber, M.; Muñiz, K.; Raabe, G. Organometallics 2000, 19, 1648.
  (h) Bolm, C.; Kesselgruber, M.; Raabe, G. Organometallics 2002, 21, 707.
  (i) Genet, C.; Canipa, S. J.; O'Brein, P.; Taylor, S. J. Am. Chem. Soc. 2006, 128, 9336.
  For a review on kinetic resolution:(j) Alba, A.-N.; Rios, R. Molecules 2009, 14, 4747.
  (k) Mercier, A.; Yeo, W. C.; Chou, J.; Chaudhuri, P. D.; Bernardinelli, G.; Kündig, E. P. Chem. Commun. 2009, 5227.
  (l) Mercier, A.; Urbaneja, X.; Yeo, W. C.; Chaudhuri, P. D.; Cumming, G. R.; House, D.; Bernardinelli, G.; Kündig, E. P. Chem.-Eur. J. 2010, 16, 6285.
  (m) Ogasawara, M.; Arae, S.; Watanabe, S.; Nakajima, K.; Takahashi, T. Chem.-Eur. J. 2013, 19, 4151.
5. [5]
  For reviews and book, see:
  (a) Giri, R.; Shi, B.-F.; Engle, K. M.; Maugel, N.; Yu, J.-Q. Chem. Soc. Rev. 2009, 38, 3242.
  (b) Peng, H. M.; Dai, L.-X.; You, S.-L. Angew. Chem., Int. Ed. 2010, 49, 5826.
  (c) Wencel-Delord, J.; Colobert, F. Chem.-Eur. J. 2013, 19, 14010.
  (d) Engle, K. M.; Yu, J.-Q. J. Org. Chem. 2013, 78, 8927.
  (e) Zheng, C.; You, S.-L. RSC Adv. 2014, 4, 6173.
  (f) Ye, B.; Cramer, N. Acc. Chem. Res. 2015, 48, 1308.
  (g) You, S.-L. Asymmetric Functionalization of C-H Bonds, RSC, Cambridge, U.K., 2015.
  (h) Gao, D.-W.; Gu, Q.; Zheng, C.; You, S.-L. Acc. Chem. Res. 2017, 50, 351.
  (i) Newton, C. G.; Wang, S.-G.; Oliveira, C. C.; Cramer, N. Chem. Rev. 2017, 117, 8908.
6. [6]
7. [7]
  Xia, J.-B.; You, S.-L. Organometallics 2007, 26, 4869. doi: 10.1021/om700806e
8. [8]
  Takebayashi, S.; Shizuno, T.; Otani, T.; Shibata, T. Beilstein J. Org. Chem. 2012, 8, 1844. doi: 10.3762/bjoc.8.212
9. [9]
  Siegel, S.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1997, 36, 2456. doi: 10.1002/(ISSN)1521-3773
10. [10]
  (a) Sokolov, V. I.; Troitskaya, L. L. Chimia 1978, 32, 122.
  (b) Sokolov, V. I.; Troitskaya, L. L.; Reutov, O. A. J. Organomet. Chem. 1979, 182, 537.
  (c) Günay, M. E.; Richards, C. J. Organometallics 2009, 28, 5833.
11. [11]
  (a) Shi, B.-F.; Maugel, N.; Zhang, Y.-H.; Yu, J.-Q. Angew. Chem., Int. Ed. 2008, 47, 4882.
  (b) Shi, B.-F.; Zhang, Y.-H.; Lam, J. K.; Wang, D.-H.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 460.
  (c) Wasa, M.; Engle, K. M.; Lin, D. W.; Yoo, E. J.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 19598.
  (d) Musaev, D. G.; Kaledin, A.; Shi, B.-F.; Yu, J.-Q. J. Am. Chem. Soc. 2012, 134, 1690.
  (e) Xiao, K.-J.; Lin, D. W.; Miura, M.; Zhu, R.-Y.; Gong, W.; Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2014, 136, 8138.
  (f) Chu, L.; Xiao, K.-J.; Yu, J.-Q. Science 2014, 346, 451.
  (g) Chan, K. S. L.; Fu, H.-Y.; Yu, J.-Q. J. Am. Chem. Soc. 2015, 137, 2042.
  (h) Laforteza, B. N.; Chan, K. S. L.; Yu, J.-Q. Angew. Chem., Int. Ed. 2015, 54, 11143.
  (i) Xiao, K.-J.; Chu, L.; Yu, J.-Q. Angew. Chem., Int. Ed. 2016, 55, 2856.
  (j) Xiao, K.-J.; Chu, L.; Chen, G.; Yu, J.-Q. J. Am. Chem. Soc. 2016, 138, 7796.
12. [12]
  Gao, D.-W.; Shi, Y.-C.; Gu, Q.; Zhao, Z.-L.; You, S.-L. J. Am. Chem. Soc. 2013, 135, 86. doi: 10.1021/ja311082u
13. [13]
  Cheng, G.-J.; Chen, P.; Sun, T.-Y.; Zhang, X.; Yu, J.-Q.; Wu, Y.-D. Chem. Eur. J. 2015, 21, 11180. doi: 10.1002/chem.v21.31
14. [14]
  Gair, J.-J.; Haines, B.-E.; Filatov, A.-S.; Musaev, D.-G.; Lewis, J.-C. Chem. Sci. 2017, 8, 5746. doi: 10.1039/C7SC01674C
15. [15]
  Pi, C.; Li, Y.; Cui, X.-L.; Zhang, H.; Han, Y.-B.; Wu, Y.-J. Chem. Sci. 2013, 4, 2675. doi: 10.1039/c3sc50577d
16. [16]
  Shi, Y.-C.; Yang, R.-F.; Gao, D.-W.; You, S.-L. Beilstein J. Org. Chem. 2013, 9, 1891. doi: 10.3762/bjoc.9.222
17. [17]
  Zhang, H.; Cui, X.-L.; Yao, X.-Y.; Wang, H.; Zhang, J.-Y.; Wu, Y.-J. Org. Lett. 2012, 14, 3012. doi: 10.1021/ol301063k
18. [18]
  Gao, D.-W.; Gu, Q.; You, S.-L. J. Am. Chem. Soc. 2016, 138, 2544. doi: 10.1021/jacs.6b00127
19. [19]
  Pi, C.; Cui, X.-L.; Liu, X.-Y.; Guo, M.X.; Zhang, H.-Y.; Wu, Y.-J. Org. Lett. 2014, 16, 5164. doi: 10.1021/ol502509f
20. [20]
  Gao, D.-W.; Yin, Q.; Gu, Q.; You, S.-L. J. Am. Chem. Soc. 2014, 136, 4841. doi: 10.1021/ja500444v
21. [21]
  Fukuzawa, S.-I.; Yamamoto, M.; Hosaka, M.; Kikuchi, S. Eur. J. Org. Chem. 2007, 5540.
22. [22]
  Deng, R.; Huang, Y.; Ma, X.; Li, G.; Zhu, R.; Wang, B.; Kang, Y.-B.; Gu, Z. J. Am. Chem. Soc. 2014, 136, 4472. doi: 10.1021/ja500699x
23. [23]
  Zhang, S.; Lu, J.; Ye, J.; Duan, W.-L. Chin. J. Org. Chem. 2016, 36, 752(in Chinese).
24. [24]
  (a) Nottingham, C.; Müller-Bunz, H.; Guiry, P. J. Angew. Chem., Int. Ed. 2016, 55, 11115.
  (b) Nottingham, C.; Müller-Bunz, H.; McGlinchey, M. J.; Guiry, P. J. Eur. J. Org. Chem. 2017, 2848.
25. [25]
  (a) Ma, X.; Gu, Z. RSC. Adv. 2014, 4, 36241.
  (b) Liu, L.; Zhang, A.-A.; Zhao, R.-J.; Li, F.; Meng, T.-J.; Ishida, N.; Murakami, M.; Zhao, W.-X. Org. Lett. 2014, 16, 5336.
26. [26]
  Gao, D.-W.; Zheng, C.; Gu, Q.; You, S.-L. Organometallics 2015, 34, 4618. doi: 10.1021/acs.organomet.5b00730
27. [27]
  Gao, D.-W.; Gu, Y.; Wang, S.-B.; Gu, Q.; You, S.-L. Organometallics 2016, 35, 3227. doi: 10.1021/acs.organomet.6b00569
28. [28]
  (a) Shibata, T.; Shizuno, T. Angew. Chem., Int. Ed. 2014, 53, 5410.
  (b) Takebayashi, S.; Shibata, T. Organometallics 2012, 31, 4114.
29. [29]
  (a) Shibata, T.; Shizuno, T.; Sasaki, T. Chem. Commun. 2015, 51, 7802.
  (b) Zhang, Q.-W.; An, K.; Liu, L.-C.; Yue, Y.; He, W. Angew. Chem., Int. Ed. 2015, 54, 6918.
  (c) Murai, M.; Matsumoto, K.; Takeuchi, Y.; Takai, K. Org. Lett. 2015, 17, 3102.
30. [30]
  Wang, S.-B.; Zheng, J.; You, S.-L. Organometallics 2016, 35, 1420. doi: 10.1021/acs.organomet.6b00020
31. [31]
  Guimond, N.; Gouliaras, C.; Fagnou, K. J. Am. Chem. Soc. 2010, 132, 6908. doi: 10.1021/ja102571b
32. [32]
  Urbano, A.; Hernández-Torres, G.; del Hoyo, A. M.; Martínez-Carrión, A.; Carre o, M. C. Chem. Commun. 2016, 52, 6419. doi: 10.1039/C6CC02624A
33. [33]
  Shibata, T.; Uno, N.; Sasaki, T.; Kanyiva, K. S. J. Org. Chem. 2016, 81, 6266. doi: 10.1021/acs.joc.6b00825
34. [34]
  Fürstner, A.; Mamane, V. J. Org. Chem. 2002, 67, 6264. doi: 10.1021/jo025962y
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