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Catellani Reaction

PPT of the catellani reaction

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Catellani Reaction

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  1. Catellani Reaction: A Winning Combination of Aromatic C-H Bond Functionalization Presented By RavirajAnandaThorat (1710227) Thesis Supervisor: Prof.Sangit Kumar Department of Chemistry IISER Bhopal

  2. Outline Introduction • Introduction • Catellani and its Catalytic Cycle • Synthetic Applications • Summary

  3. Introduction C−H Bond Functionalization Conventional C−C Bond Coupling Reaction Mizoroki-Heck E-ichiNegishi Suzuki-Miyaura Kuhl et al. Angew. Chem. Int. Ed.2012, 51, 10236

  4. Introduction: Prof. Marta Catellani • 1971 Ph.D. (Prof. G. Casnati, University of Parma, Italy) • 1977-78 Post-doc, Prof. J. Halpern (University of Chicago, USA) • 1990-persent, Prof. University of Parma, Italy • Catellani reaction was discovered in 1997 • Involves one-pot reaction • Three C-C bonds formation • Disubstitued vinylarenes synthesis Catellani, M. & co-workers Angew. Chem. Int. Ed. 1997, 36, 119

  5. Origin of Idea Inoue, N. et al, Tetrahedron Lett. 1974, 15,647

  6. Features • Dual catalyst pathway • Role of Norbonene: catalyst, reactant and mediator • Enables the selective functionalization of ortho, ipso, meta and even site selective paraof aryl halide

  7. Carbopalladation of Norbornene Inability of bicycle system for β-hydride elimination

  8. Simplified Catalytic Cycle Dong, G. J. Am. Chem. Soc. 2018, 140, 8551

  9. Synthetic Applications Mizoroki-Heck Catellani, M. Angew. Chem. Int. Ed. 1997, 36, 119 Suzuki-Miyaura Catellani, M. Chem. Comm. 2000, 157

  10. Synthetic Application in Alkyne Insertion Alkyne Insertion Catellani, M. Org. Lett. 2001, 3, 23 Norbornene as Reactant Lautens, M. Angew. Chem. Int. Ed.2009, 48, 1447

  11. Catalytic Cycle Lautens, M. Angew. Chem. Int. Ed.2009, 48, 1447

  12. Functioanlization of Indole Previous Approach Glorius, Kanai and others Regioselective C-2 Alkylation of Indole Bach, T. & co-workers J. Am. Chem. Soc. 2012, 134, 14563

  13. Functioanlization of Indole: Mechanism Bach, T. & co-workers J. Am. Chem. Soc. 2012, 134, 14563

  14. Directing Group Approach Previous Approach Dauglis, Chatani and others End on Template Yu, J.Q. co-worker Nature. 2012, 486, 519

  15. Ligand - Enabled Meta C-H Activation NBE as transient mediator catch & release pathway Yu, J.Q. co-worker Nature. 2015, 519 , 334

  16. Formation of ipso-C-Heteroatom Bonds Previous Approach Ritter, T. & co-workers J. Am. Chem. Soc.2015, 137, 3775

  17. Discovery of Borono Catellani Reaction Zhou, Q. & co-workers J. Am. Chem. Soc., 2015, 137, 3775

  18. Cleavage of the C(O)−S Bond of Thioesters Liebeskind-Srogl coupling Liebeskind andSrogl, J. Am. Chem. Soc. 2000, 122, 11260 Zhenhua, G. & co-workers,J.Am. Chem. Soc. 2016, 138, 7456

  19. Epoxides as Alkylating Reagents • Highly reactive and strained rings • Small heterocycle such as epoxides and aziridines present in bioacitive natural product. Zhou, Q. & co-workers Angew. Chem. Int. Ed. 2018, 57, 3444

  20. Synthesis of Tetrahydroisoquinolines Zhou, Q. & co-workers Angew. Chem. Int. Ed.2018, 130, 11146

  21. Complementary Site-selectivity in AreneFunctioanlization Dong, G. & co-workers Nature, 2018, 10, 866

  22. Applications Dong, G. & co-workers Nature. 2018, 10, 866

  23. Installation of Acyl Group on Aryl Dong, G. & co-workers Angew. Chem. Int. Ed. 2015, 54, 12664

  24. Synthesis of Indenone Chatani, N.& co-workers J. Am. Chem. Soc. 2007, 129, 5766 Dong, G & co-workers Angew. Chem. Int. Ed. 2019, 58, 2144

  25. Summary • This methodology has the potential to simplify reactions by avoiding the use of prefunctionalized reagents. • The synergistic interplay of Palladium & norbornene facilitate ortho & ipso C-H functionalization in single operation • Late-stage functionalization of complex & bioactive molecules.

  26. Acknowledgement • Thesis Supervisor : Professor Sangit Kumar • Director IISER Bhopal • Faculty members • Department of Chemistry • CSIR for Fellowship • IISER Bhopal • Lab mates, Friends and Parents

  27. Back up slide

  28. Progress of Reaction Dong, G. J. Am. Chem. Soc. 2018, 140, 8551

  29. Liebeskind-Srogl coupling

  30. It is an efficient one pot synthesis for making carbon-heteroatom bond • ANP intermediate ( five membered palladacycle) plays crucial role in Catellani reactions • Late-stage functionalization of complex bioactive molecules • Asymmetric catalysis and Pd/norbornene chemistry is the possibility of creating • asymmetric sequence with exciting applications • Unexplored of norbornadiene?

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