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Rhodium Catalyzed Direct C-H Functionalization

Rhodium Catalyzed Direct C-H Functionalization. 陈殿峰 2012.10.13. Outline :. Introduction Oxidative coupling Nucleophilic Addition Other Reactions Conclusion. 1. Introduction. 2. Oxidative Coupling. Heck Type. DG =. Oxidizing DG.

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Rhodium Catalyzed Direct C-H Functionalization

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  1. Rhodium Catalyzed Direct C-H Functionalization 陈殿峰 2012.10.13

  2. Outline: • Introduction • Oxidative coupling • Nucleophilic Addition • Other Reactions • Conclusion

  3. 1. Introduction

  4. 2. Oxidative Coupling Heck Type DG = Oxidizing DG See: F. Glorius, J. A. Ellman, Sukbok Chang,T. Satoh, M. Miura Z.-J. Shi, X.-W. Li, T. Rovis, N. Cramer

  5. 2. Oxidative Coupling Arylation Double C-H activation F.Glorious, Angew. Chem. Int. Ed. 2012, 51, 2247 M. Miura, Angew. Chem. Int. Ed.2012, 51, 5359

  6. 2. Oxidative Coupling Alkynylation Alkynylation Y= DG T. Satoh, M. Miura, Angew. Chem. Int. Ed. 2008, 47, 4019-4022

  7. 2. Oxidative Coupling Alkynylation Alkynylation C. Zhu, Chem. Eur. J. 2011, 17, 12591-12595

  8. 2. Oxidative Coupling Alkynylation B.-Q. Wang, J. Am. Chem. Soc.,  2012, 134,16163 Halogenation Path a : nucleophilic addition Path b : high oxidation-state Rh(V) F. Glorius, J. Am. Chem. Soc.,2012,134, 8298-8301

  9. 2. Oxidative Coupling Oxidizing DG Background J. F. Hartwig J. Am. Chem. Soc, 2010, 132, 3676 W.-Y. Yu, J. Am. Chem. Soc, 2010, 132,12862 X.-L. Cui, Y.-J. Wu, J. Am. Chem. Soc.,  2009, 131,13888

  10. 2. Oxidative Coupling Oxidizing DG N. Guimond, J. Am. Chem. Soc., 2010, 132, 6908 N. Guimond, J. Am. Chem. Soc, 2011, 133, 6449

  11. 2. Oxidative Coupling Oxidizing DG C-N Cleavage Z.-J. Shi, Angew. Chem. Int. Ed., 2012, 52, 3948

  12. 2. Oxidative Coupling For Rh catalyzed oxidative coupling: 1). Rh(III) is generally efficient catalyst because its high oxidation-state facilitates β-elimination； 2). Versatile DGs have been well established whereas DG-free coupling reactions are still rare; 3). The fact that more than stoichiometric metal-oxidants (Cu2+, Ag+) are generally needed callsfor eco-friendly pathways (air). 4). Harsh reaction conditions (high temprature, excess oxidant, strong base or acid) lead to poor functional group tolerence. 5). Limited examples involving sp3 C-H activation are reported.

  13. 3. Nucleophilic Addition Direct Addition

  14. 3. Nucleophilic Addition Direct Addition Direct Addition Direct Addition

  15. 3. Nucleophilic Addition Direct Addition R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2008, 130, 3645 R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2012, 134, 4064

  16. 3. Nucleophilic Addition Direct Addition C.-H. Cheng, Angew. Chem. Int. Ed.,2012, 51, 197 S.-M. Ma, J. Am. Chem. Soc.2012, 134, 9597

  17. 3. Nucleophilic Addition Direct Addition Others Acceptors Imine: Z.-J. Shi, Org. Lett, 2012, 14, 4498 R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc, 2011. 133, 1248 J. Am. Chem. Soc, 2012. 134, 1482 Aldehyde: Isocyanates: Z.-J. Shi, Org. Lett, 2012, 14, 636 Org. Lett, 2012, 14, 4498 R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc, 2011. 133, 11430

  18. 3. Nucleophilic Addition Delayed Addition Notes: 1.DG as acceptors; 2. Strained direct addition T. Satoh, M. Miura. Chem. Commun. 2009, 5141

  19. 3. Nucleophilic Addition Delayed Addition P.-J. Zhao, Chem. Eur. J.2010, 16, 2619 N. Cramer, Angew. Chem. Int. Ed, 2010, 49, 8181 N. Cramer, Angew. Chem. Int. Ed, 2011, 50, 11098.

  20. 3. Nucleophilic Addition Delayed Addition C.-H. Cheng, Angew. Chem. Int. Ed, 2011, 50, 4169 F. Glorius, J. A m. Chem. Soc.2011, 133, 2154

  21. 3. Nucleophilic Addition For nucleophilic C-Rh : 1). Rh(I)/Rh(III) are both efficient catalysts； 2). More type of acceptors are needed to developed and three components reaction has not been reported; 3). Alkenes or other moities that could insert C-Rh bond may take the place of alkynes 4). Limited assymetric examples have been demonstrated, which indicates, in a way, the limitation of existing chiral ligands.

  22. 4. Other Reactions Nucleophilic addition via C-C Cleavage M. Murakami, J. A m. Chem. Soc. 2007, 129, 12086 M. Murakami, J. A m. Chem. Soc.2012, 134, ASAP. Oxidative Coupling via C-C Cleavage Z.-J. Shi, J. A m. Chem. Soc.2011, 133, 15244.

  23. 4. Other Reactions Carboacylation of Olefins G.-B. Dong, Angew. Chem. Int. Ed, 2012, 51, 7767 Ring Open of VCP Z.-X. Yu, J. A m. Chem. Soc.2011, 134, 398. Z.-X. Yu, Angew. Chem. Int. Ed, 2011, 50, 2144

  24. 4. Other Reactions Z.-X. Yu, J. A m. Chem. Soc.2010, 132, 4542.

  25. 5. Conclusion: 1). Rh(I)/Rh(III) are versatile catalysts towards C-H bond activation; 2). Necessary DGs limite the substrates scope; 3). Direct sp3 C-H functionalization remains challenging; 4). Mild reaction conditions are demanded for better functional group tolerence. 5). New chiral ligands or novel asymmetric catalytic circles would highlight Rh catalyzed C-H activation.

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