1 / 51

Trost’s Palladium Catalysed Asymmetric Allylic Alkylation (Pd-AAA)

Trost’s Palladium Catalysed Asymmetric Allylic Alkylation (Pd-AAA). Literature Meeting Charette’s group Miguel St-Onge October 9 th , 2007. Presentation. Trost and Palladium p - allyl complexes Stereochemistry of oxidative addition and nucleophilic attack Counter anion effects

gil-cohen
Télécharger la présentation

Trost’s Palladium Catalysed Asymmetric Allylic Alkylation (Pd-AAA)

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. Trost’s Palladium Catalysed Asymmetric Allylic Alkylation(Pd-AAA) Literature Meeting Charette’s group Miguel St-Onge October 9th, 2007

  2. Presentation • Trost and Palladium • p-allyl complexes • Stereochemistry of oxidative addition and nucleophilic attack • Counter anion effects • Synvs anti complexes • Nucleophilic approach on allyl terminus • Ligands and cartoon model • Classes of enantiodiscrimination processes • Types of nucleophiles and their application to total synthesis • Exceptions to the model • AAA with other metals • Total synthesis of Tipranavir • Conclusion

  3. Pr. Barry M. Trost • Born in 1941 in Philadelphia • Received B.A. From University of Pennsylvania (1962) • Received Ph.D. at MIT under H.O. House’s supervision (1965) • Professor of chemistry at University of Wisconsin (1969) • Vilas research professor of chemistry (1982) • Professor of chemistry at Standford University (1987) • Takami professor of humanities and sciences (1990) • 803 publications (2006) • 38 honors and awards • 14 Patents Barry Trost web page at www.stanford.edu/group/bmtrost

  4. Palladium • Discovered in 1803 by William Hyde Wollaston • Isolated from (NH4)2PtCl6 • Name comes from Greek goddess of wisdom, Pallas or Palladion • Atomic number 46 • [Kr] 4d10 • Pd0 = 18e square planar complexes • Pd(II) = 14e square planar complexes

  5. -Allyl Palladium Complex and C-C Bond Formation Trost, B. M.*; Weber, L. J.Am.Chem.Soc. 1975, 97, 1611-1612.

  6. Trost’s Study Trost, B.M; Weber, L. J. Am. Chem. Soc.1975, 97, 1611-1612

  7. Study conclusion • Conclusions: • Stereospecificity of allylic alkylation has potentially important consequences in the application of the method for the creation of stereochemistry in acyclic and macrocyclic systems. • - Alkylation occurs on the face of the -allyl unit opposite to that of the palladium and use of soft nucleophiles are required for successful alkylation

  8. Stereochemistry of Oxidative Addition Hayashi, T.*; Hagihara, T.; Konishi, M.; Kumada, M. J. Am. Chem. Soc. 1983, 105, 7768-7770.

  9. Stoichiometric vs Catalytic • Conclusions: • Oxidative addition of palladium proceed with inversion of configuration and addition on -allyl palladium proceed also with inversion of configuration. • Net retention of configuration also occurs in enantiomeric catalytic system

  10. Catalytic Cycle

  11. Counter Anion Effects Amatore, C.; Jutand, A.; M’Barki, M. A.; Meyer, G.; Mottier, L. Eur. J. Inorg. Chem.2001, 873. Cantat, T.; Génin, É.; Giroud, C.; Meyer, G.; Jutand, A.* J. Org. Chem.2003, 687, 365-376.

  12. Syn Complex vs Anti Complex (p-s-p equilibration) Trost, B.M.; Machacek, M.R.; Aponik, A. Acc. Chem. Res.2006, 39, 747-760.

  13. Nucleophile Approach • Nucleophile addition is considered as a SN2-like displacement • Attack must be anti to the Pd leaving group (180o) • High impact for ligand working model analysis

  14. Allyl Terminus Less substituted terminus More substituted terminus Trost, B.M.; Machacek, M.R.; Aponik, A. Acc. Chem. Res.2006, 39, 747-760.

  15. Redesign Catalytic Cycle

  16. Successful Ligands Tognie, A.; Breutel., C.; Schnyder, A.; Spindler, F.; Landert, H.; Tijani, A J. Am. Chem. Soc. 1994, 116, 4062-4066. Pfaltz, A Acc. Chem. Res. 1993, 26, 339-345. Evans, D.A.; Campos, K.R.; Tedros, J.S.; Michael, F.E.; Gagné, M.R. J. Am. Chem. Soc. 2000, 122, 7905-7920. Faller, J.W.; Wilt, J.C. Organometallics, 2005, 24, 5076-5083. Morimoto, T.; Tachibana, K.; Achiwa, K. Synlett, 1997, 783-785.

  17. Trost’s Classic Ligands

  18. Cartoon Model Trost, B.M.; Toste, F.D. J. Am. Chem. Soc., 1999, 121, 4545-4554. Lloyd-Jones G.C. Et. Al. Pure Appl. Chem., 2004, 76, 589-601.

  19. Classes of Enantiodiscriminating Processes Ionization of the leaving group • Class A- Desymmetrization of meso diester • Class B- Desymmetrization of prochiral leaving group on the same carbon • Class C- Unsymmetrical p-allyl Pd complexes (achiral) Addition of the nucleophile • Class D- Meso-like p-allyl Pd complex • Class E- Unsymmetrical p-allyl Pd complexes (chiral)

  20. Class A- Desymmetrization of meso Diester Trost, B.M.; Dudash, J., Jr.; Dirat, O. Chem-Eur. J. 2002, I81, 259-268. Trost, B.M.; Patterson, D.E., J. Org. Chem., 1998, 63, 1339-1341.

  21. Class B- Desymetrisation of Prochiral Leaving Group on the Same Carbon Trost, B.M.; Lee, C.B. J. Am. Chem. Soc. 1998, 120, 6818-6819.

  22. Class B- Desymmetrization of Prochiral Leaving Group on the Same Carbon Trost, B.M.; Lee, C.B. J. Am. Chem. Soc. 1998, 120, 6818-6819.

  23. Class C- Unsymmetrical p-Allyl Pd Complexes (Achiral) Trost, B.M.; Machacek, M.R. Angew. Chem., Int. Ed.2002, 41, 4693-4697.

  24. Class C- Unsymmetrical p-Allyl Pd Complexes (Achiral) Trost, B.M.; Machacek, M.R. Angew. Chem., Int. Ed.2002, 41, 4693-4697.

  25. Class D- Meso-like p-Allyl Pd Complex Trost, B.M.; Dudash, J., Jr.; Hembre, E.J. Chem.-Eur. J. 2001, 16, 1619-1629.

  26. Class D- Meso-like p-Allyl Pd Complex Trost, B.M.; Dudash, J., Jr.; Hembre, E.J. Chem.-Eur. J. 2001, 16, 1619-1629.

  27. Class E- Unsymmetrical p-Allyl Pd Complexes (Chiral Acyclic Substrate) Trost, B.M.; Bunt, R.C.; Lemoine, R.C.; Calkins, T.L. J. Am. Chem. Soc. 2000, 122, 5968-5976.

  28. Class E- Unsymmetrical p-Allyl Pd Complexes (Chiral Cyclic Substrate) Trost, B.M.; Toste, F.D. J. Am. Chem. Soc.2003, 125, 3090-3100.

  29. Lactone Isomerization Trost, B.M.; Toste, F.D. J. Am. Chem. Soc.2003, 125, 3090-3100.

  30. Chirality at the Nucleophile Trost, B.M.; Radinov, R.; Grenzer, H.M. J. Am. Chem. Soc. 1997, 119, 7879-7880. Trost, B.M.; Schroeder, G.M.; Kristensen, J Angew. Chem., Int. Ed.2002, 41, 3492-3495.

  31. Carbon Nucleophiles in Total Synthesis Malonate type: Chapsal, B.D.; Ojima, I. Org. Lett., 2006, 8, 1395-1398.

  32. Carbon Nucleophiles in Total Synthesis Sulfone Type: Nitro type: Trost, B. M.; Chupak, L. S.; Lubbers J. Am. Chem. Soc. 1998, 120, 1732-1740. Trost, B. M.; Surivet, J.-P. Angew. Chem., Int. Ed.2000, 39, 3122-3124.

  33. Oxygen Nucleophiles in Total Synthesis Primary alcohols: Carboxylates: Trost, B. M.; Weiping, T.; Schulte, J. L. Org. Lett. 2000, 2, 4013-4015. Trost, B. M.; Kondo, Y. Tet. Let.1991, 32, 1613.

  34. Oxygen Nucleophiles in Total Synthesis Phenols Trost, B. M.; Toste, F. D. J. Am. Chem. Soc.1998, 120, 9074-9075. Trost, B. M., Tang, W. J. Am. Chem. Soc., 2002, 124, 14542-14543.

  35. Nitrogen Nucleophiles Amines • Mono versus bisalkylation of primary amines • Regioselectivity on Pd p-allyl system • Speed of nucleophile versus p-s-p equilibration Trost, B. M.; Krische, M. J.; Radinov, R.; Zanoni, G. J. Am. Chem. Soc. 1996, 118, 6297-6298. You, S. L.; Zhu, X. Z.; Luo, Y. M.; Hou, X. L.; Dai, L. X. J. Am. Chem. Soc. 2001, 123, 7471-7472.

  36. Nitrogen Nucleophiles in Total Synthesis Azides Trost, B. M.; Pulley, S.R. J. Am. Chem. Soc 1995, 117, 10143-10144. Trost, B. M.; Cook, G. R. Tet. Lett., 1996, 37, 7485-7488.

  37. Nitrogen Nucleophiles in Total Synthesis Sulfonamide Trost, B. M.,; Oslob, J. D.; J. Am. Chem. Soc. 1999, 121, 3057-3064. Mori, M.; Nakanishi, M.; Kajishima, D.; Sato, Y. Org. Lett.2001, 3, 1913-1916.

  38. Nitrogen Nucleophiles in Total Synthesis Imides Trost, B. M.,; Patterson, D. E.; Chem. Eur. J.1999, 5, 3279 Buschmann, N.; Rueckert, A.; Blechert, S. J. Org. Chem.2002, 67, 4325-4329.

  39. Nitrogen Nucleophiles in Total Synthesis Trost, B. M.; Shi, Z. J. Am. Chem. Soc. 1996, 118, 3037-3038. Trost, B. M.; Madsen, R.; Guile, S. D.; Tet. Lett., 1997, 38, 1707-1710.

  40. Sulfur Nucleophiles Pd -AAA Trost, B. M.; Organ, M. G.; O’Doherty, G. A. J. Am. Chem. Soc.1995, 117, 9662-9670. Trost, B. M.; Crawley, M. L.; Lee, C. B. J. Am. Chem. Soc.2000, 122,6120-6121.

  41. Exceptions Trost, B. M.; Toste, D. F. J. Am. Chem. Soc. 2000, 122, 11262-11263. Trost, B.M.; Machacek, M.R.; Aponick, A. Acc. Chem. Res.2006, 39, 747-760.

  42. Exceptions Trost, B.M.; Machacek, M.R.; Aponick, A. Acc. Chem. Rev.2006, 39, 747-760.

  43. Exceptions Trost, B.M.; Gunzner, J.L.; Dirat, O.; Rhee, Y. H. J. Am. Chem. Soc.2002, 124, 10396-10415.

  44. AAA with Other Metals: Tungsten Lloyd-Jones, G.C.; Pfaltz, A. Angew.Chem., Int. Ed., 1995, 34, 462. Co, T.T.; Paek, S.W.; Shim, S.C.; Cho, C.S.; Kim, T.-J.; Choi, D.W.; Kang, S.O.; Jeong, J.H Organometallics, 2002, 22, 1475-1482.

  45. AAA with Other Metals: Iridium Ohmura, T.; Hartwig J.F. J. Am. Chem. Soc. 2002, 124, 15164-15165. Kiener, C.A.; Shu, C.; Incarvito, C.; Hatrwig, J.F. J. Am. Chem. Soc. 2003, 125, 14272-14273.

  46. Novel Iridium Utilisation • Preparation of -Substituted Allylboronates by Chemoselective Iridium-Catalyzed Asymmetric Allylic Alkylation of 1-Propenylboronates - Peng, F.; Hall*, D. G. Tet. Lett.2007, 18, 3305-3309 • Salt-Free Iridium-CatalyzedAsymmetricAllylicAminationswithN,N-Diacylamines and ortho-Nosylamide as AmmoniaEquivalents - Weihofen, R.; Tverskoy, O.; Helmchen, G.; Angew. Chem., Int. Ed.2006, 33, 5546-5549 • Very Efficient Phosphoramidite Ligand for Asymmetric Iridium-CatalyzedAllylic Alkylation - Alexakis*, A.; Polet, D.; Org. Lett.2004, 20, 3529-3532 • Regio- and Enantioselective Iridium-Catalyzed Allylic Alkylation with In Situ Activated P,C-Chelate Complexes - Lipowsky, G.; Miller, N.; Helmchen, G. Angew. Chem., Int. Ed.2004, 43, 4595 –4597

  47. AAA with Other Metals: Molybdenum Trost, B.M.; Dogra, K. J. Am. Chem. Soc. 2002, 124, 7256-7257.

  48. Molybdenum AAA Transition State Krska, S. W.; Hughes, D. L.; Reamer, R. A.; Mathre, D. J.; Sun, Y.; Trost, B. M. J. Am. Chem. Soc. 2002, 124 (43), 12656-12657.

  49. Synthesis of Tipranavir (Aptivus) Trost, B.M.; Andersen, N.G. J. Am. Chem. Soc.2002, 124, 14320-14321.

  50. Synthesis of Tipranavir (Aptivus) 15 steps, 25%yield Trost, B.M.; Andersen, N.G. J. Am. Chem. Soc.2002, 124, 14320-14321.

More Related