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Patrick Robichaux Tang Group University of Wisconsin-Madison Department of Chemistry Literature Seminar 04/28/2011

A Recent Inquiry into the Preparation and Practical Application of Benzyne. Patrick Robichaux Tang Group University of Wisconsin-Madison Department of Chemistry Literature Seminar 04/28/2011. Overview. History. Preparation. Regioselectivity. Application. Overview. History.

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Patrick Robichaux Tang Group University of Wisconsin-Madison Department of Chemistry Literature Seminar 04/28/2011

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  1. A Recent Inquiry into the Preparation and Practical Application of Benzyne Patrick Robichaux Tang Group University of Wisconsin-Madison Department of ChemistryLiterature Seminar 04/28/2011

  2. Overview History Preparation Regioselectivity Application

  3. Overview History Preparation Regioselectivity Application

  4. Evidence for Benzyne Roberts, J. D.; Simmons, H. E.; Carlsmith, L. A.; Vaughan, C. W. J. Am. Chem. Soc.1953,75, 3290.

  5. Neutral Benzyne Intermediate? Roberts, J. D.; Simmons, H. E.; Carlsmith, L. A.; Vaughan, C. W. J. Am. Chem. Soc. 1953,75, 3290.

  6. Singlet or Triplet? • hν = diradical? • Benzyne actually singlet • singlet-triplet splitting of 37.5 kcal/mol • lifetime at least 20 ms Wittig, G.; Ebel, H. F. Angew. Chem.1960,72, 564. Wentrup, C. Aust. J. Chem.2010,63, 979.

  7. Overview History Preparation Regioselectivity Application

  8. Traditional Formation of Benzyne Kitamura, T. Aust. J. Chem.2010,63, 987. Wentrup, C. Aust. J. Chem.2010,63, 979. Pellissier, H.; Santelli, M. Tetrahedron2003,59, 701.

  9. Synthesis of Silyltriflate Bronner, S. M.; Garg, N. K. J. Org. Chem.2009, 74, 8842-8843. Tadross, P. M.; Gilmore, C. D.; Bugga, P.; Virgil, S. C.; Stoltz, B. M. Org. Lett.2010, 12, 1224-1227. Wu, Q.-c.; Li, B.-s.; Shi, C.-q.; Chen, Y.-x. HechengHuaxue2007, 111. Himeshima, Y.; Sonada, T.; Kobayashi, H. Chem. Lett.1983, 1211. • Peña, D.; Cobas, A.; Pérez, D.; Guitián, E. Synthesis2002. 1454.

  10. Activation Domino • Silyl protecting group tolerant Ikawa, T.; Nishiyama, T.; Nosaki, T.; Takagi, A.; Akai, S. Org. Lett.2011, 13, 1730.

  11. New Method: C-H activation CHEAP! • highly solvent and concentration dependent • Optimized conditions: Pd(OAc)2 (10 mol %) • Cu(OAc)2 (0.75 equiv.) • 1,10-phenanthroline (10 mol %) • K2HPO4 (2 equiv.) , TBAB (1 equiv.) • sulfonane, 4 Å MS <47% yield + side products Cant, A. A.; Roberts, L.; Greaney, M. F. Chemical Communications2010, 46, 8671-8673.

  12. Overview History Preparation Regioselectivity Application

  13. Regioselectivity: Sterics Diemer, V.; Begaud, M.; Leroux, F. R.; Colobert, F. Eur. J. Org. Chem.2011, 341.

  14. Regioselectivity: Sterics vs. Electronics Diemer, V.; Begaud, M.; Leroux, F. R.; Colobert, F. Eur. J. Org. Chem.2011, 341.

  15. Regioselectivity: Electronics Diemer, V.; Begaud, M.; Leroux, F. R.; Colobert, F. Eur. J. Org. Chem.2011, 341.

  16. Distortion/Interaction Model Cheong, P. H. Y.; Paton, R. S.; Bronner, S. M.; Im, G. Y. J.; Garg, N. K.; Houk, K. N. J. Am. Chem. Soc. 2010,132, 1267. Im, G. Y. J.; Bronner, S. M.; Goetz, A. E.; Paton, R. S.; Cheong, P. H. Y.; Houk, K. N.; Garg, N. K. J. Am. Chem. Soc. 2010, 132, 17933.

  17. Reactivity of Indolyne Systems Im, G. Y. J.; Bronner, S. M.; Goetz, A. E.; Paton, R. S.; Cheong, P. H. Y.; Houk, K. N.; Garg, N. K. J. Am. Chem. Soc. 2010, 132, 17933.

  18. Overview History Preparation Regioselectivity Application

  19. Nucleophilic Additions

  20. Acyl-Alkylation of Arynes Tambar, U. K.; Stoltz, B. M. J. Am. Chem. Soc. 2005,127, 5340.

  21. Acyl-Alkylation of Arynes Tambar, U. K.; Ebner, D. C.; Stoltz, B. M. J. Am. Chem. Soc. 2006,128, 11752.

  22. Indolines and Isoquinolines Gilmore, C. D.; Allan, K. M.; Stoltz, B. M. J. Am. Chem. Soc. 2008,130, 1558.

  23. Indolyne: Regioselectivity Reversal Bronner, S. M.; Goetz, A. E.; Garg, N. K. J. Am. Chem. Soc. 2011,133, 3832.

  24. Indole Synthesis Barluenga, J.; Fananas, F. J.; Sanz, R.; Fernandez, Y. Chemistry-a European Journal2002,8, 2034.

  25. Biaryl Synthesis Milne, J. E.; Buchwald, S. L. J. Am. Chem. Soc. 2004,126, 13028.

  26. Cycloadditions

  27. Enamide Cascade Feltenberger, J. B.; Hayashi, R.; Tang, Y.; Babiash, E. S. C.; Hsung, R. P. Org. Lett.2009,11, 3666.

  28. [4+2] Cycloaddition on Arene System Nishimura, T.; Nagaosa, M.; Hayashi, T. Chem.Lett.2008,37, 860.

  29. Metal Free Click Chemistry Lin, Y.; Chen, Y.; Ma, X.; Xu, D.; Cao, W.; Chen, J. Tetrahedron2011,67, 856.

  30. Indole Synthesis • Nair, V.; Kim, K. H. J. Org. Chem.1975,40, 3784.

  31. Transition Metal Reactions

  32. 3-Component Benzyne Coupling Larrosa, I.; Da Silva, M. I.; Gómez, P. M.; Hannen, P.; Ko, E.; Lenger, S. R.; Linke, S. R.; White, A. J. P.; Wilton, D.; Barrett, A. G. M. J. Am. Chem. Soc. 2006,128, 14042.

  33. 3-Component Benzyne Coupling Larrosa, I.; Da Silva, M. I.; Gómez, P. M.; Hannen, P.; Ko, E.; Lenger, S. R.; Linke, S. R.; White, A. J. P.; Wilton, D.; Barrett, A. G. M. J. Am. Chem. Soc. 2006,128, 14042.

  34. Catalytic Carbonylation Chatani, N.; Kamitani, A.; Oshita, M.; Fukumoto, Y.; Murai, S. J. Am. Chem. Soc. 2001,123, 12686.

  35. Pd-catalyzed Heck: Suzuki: Jayanth, T. T.; Jeganmohan, M.; Cheng, C.-H. Org. Lett.2005,7, 2921. Henderson, J. L.; Edwards, A. S.; Greaney, M. F. Org. Lett.2007,9, 5589.

  36. Conclusions = Image from google images

  37. Acknowledgments • Professor Weiping Tang • Tang and Hsung group • Kat Myhre • Practice Talk Attendees: • Jenny B. Werness • Dongxu Shu • Wei Zhang • Renhe Liu • Xiaoxun Li • Dr. Xingzhong Shu • Suyu Huang • Andrew G. Lohse • Kyle Dekorver

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