1 / 27

by William Schulz Bechara

by William Schulz Bechara. Charette/Collins Literature Meeting November 13 th , 2012. The History of C–H Amination.

gerry
Download Presentation

by William Schulz Bechara

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. by William Schulz Bechara Charette/Collins Literature Meeting November 13th, 2012

  2. The History of C–H Amination ¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨ Wolff M. E. Chem. Rev. 1963, 63, 55.

  3. The History of C–H Amination ¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨ ¨Hofmann made the surprising discovery that […] a tertiary amine was obtained, and this product was later shown to be octahydroindolizine.¨ (a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Hofmann, A. W. Chem. Ber. 1879, 12, 984.

  4. The History of C–H Amination ¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨ ¨Hofmann made the surprising discovery that […] a tertiary amine was obtained, and this product was later shown to be octahydroindolizine.¨ (a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Hofmann, A. W. Chem. Ber. 1879, 12, 984.

  5. Isolation of Intermediates Wolff M. E. Chem. Rev. 1963, 63, 55.

  6. Isolation of Intermediates Wolff M. E. Chem. Rev. 1963, 63, 55.

  7. Hofmann–Löffler–Freytag Reaction ¨In 1909, K. Löffler and C. Freytag extended the scope of this transformation and demonstrated the synthetic utility of the process as exemplified by their elegant synthesis of nicotine.¨ (a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Löffler, K.; Freytag, C. Chem. Ber. 1909, 42, 3427.

  8. Mechanistic Studies In 1950s and 60s… Indication that C−H bond cleavage : rate-limiting step of the reaction (a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Wawzonek, S.; Thelan, P. J. J. Am. Chem. Soc. 1950, 72, 2118. (c) Corey, E. J.; Hertler, W. R. J. Am. Chem. Soc. 1960, 78, 1657.

  9. Mechanism -Acidic Conditions : -Initiation : -Propagation : -Termination : -Basic Conditions : Wolff M. E. Chem. Rev. 1963, 63, 55.

  10. Rise of Nitrene Chemistry (a) Breslow, D. S.; Sloan, M. F. Tetrahedron Lett. 1968, 9, 5349. (b) Breslow, D. S.; Edwards, E. I.; Linsay, E. C.; Omura, H.J. Am. Chem. Soc. 1976, 98, 4268.

  11. Rise of C-H Insertion/ and C-H Activation/Amination C-H InsertionC-H Activation (a) Collet, F.; Dodd, R. H.; Dauban, P. Chem. Commun.2009, 5061. (b) Collet, F.; Lescot, C.; Dauban, P. Chem. Soc. Rev.2011, 40, 1926.

  12. Selectfluor Mediated Oxidation of Alcohols and Aldehydes Banks, R. E.; Lawrence, N. J.; Popplewell, A. L. Synlett, 1994, 831.

  13. Unexpected Selectfluor Mediated C-H Functionalization Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun.1996, 1629.

  14. Unexpected Selectfluor Mediated C-H Functionalization Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun.1996, 1629.

  15. Selectfluor Mediated C-H Functionalization Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun.1996, 1629.

  16. Proposed Mechanism - Ritter-Type C−H Amination Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun.1996, 1629.

  17. Ritter Reaction

  18. Baran… Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  19. Optimization Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  20. Optimization Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  21. C-H Amination with Inexpensive Source of Nitrogen Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  22. C-H Amination with Inexpensive Source of Nitrogen Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  23. Isomerization of cis-Decalin Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  24. Hydrolysis Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  25. Mechanistic Studies Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547.

  26. Mechanistic Hypothesis - SET (a) Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc.2012, 134, 2547. (b) Kochi, J. K. Science1967, 155, 415.

  27. F+ Mediated Oxidation of Metal; PdII / PdIV – AuI / AuIII (a) Nyffeler, P. T.; Durón, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C.-H. Angew. Chem., Int. Ed. 2005, 44, 192 . (b) Mei, T.-S.; Wang, X.; Yu, J.-Q. J. Am. Chem. Soc. 2009, 131, 10806. (c) Hull, K. L.; Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 7134. (d) Rosewall, C. F.; Sibbald, P. A.; Liskin, D. V.; Michael, F. E. J. Am. Chem. Soc. 2009, 131, 9488. (e) Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474.

More Related