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The application of alkaline metal(Ca, Sr, Ba) complex as catalyst in organic chemistry

The application of alkaline metal(Ca, Sr, Ba) complex as catalyst in organic chemistry. 2010.12.04 张文全. introduction.

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The application of alkaline metal(Ca, Sr, Ba) complex as catalyst in organic chemistry

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  1. The application of alkaline metal(Ca, Sr, Ba) complex as catalyst in organic chemistry 2010.12.04 张文全

  2. introduction Alkaline earth metals are very attractive because they are abundant and ubiquitous elements in nature and form safe compounds compared with other heavy transition metals. However, their positive use as catalysts in asymmetric synthesis is still limited. Their strong Brønsted basicity and mild Lewis acidity can influence their catalytic activity, as well as chiral modification of a complex in a positive manner.

  3. calcium The application of calcium complex in organic chemistry will show follow

  4. First example of an optically active calcium catalyst Baylis–Hillman Reaction 62 yield% 56 ee% Shiro Ikegami, Tetrahedron Letters 41 (2000) 2165

  5. Michael Reactions G. Kumaraswamy, Tetrahedron Letters 42 (2001) 8515

  6. G. Kumaraswamy, Adv. Synth. Catal. 2005, 347, 867

  7. 18-96ee% 50-quant yield% Shu Kobayashi, Angew. Chem. Int. Ed. 2009, 48, 9117

  8. Shu Kobayashi, Tetrahedron: Asymmetry 21 (2010) 1221

  9. ligand real catalyst Shu Kobayashi, J. AM. CHEM. SOC. 2010, 132, 7890

  10. Shu Kobayashi, J. AM. CHEM. SOC. 2007, 129, 5364 Shu Kobayashi, J. AM. CHEM. SOC. 2008, 130, 13321 Shu Kobayashi, O.L. 2008, Vol. 10, No. 5, 807

  11. Catalytic cycle of the 1,4-addition reaction

  12. Two Possible Reaction Mechanisms of the [3 + 2] Cycloaddition Reaction

  13. cis/trans=2/1 so stepwise is possible

  14. Friedel-Craft Reaction ArH = electrion-rich Aromatic Meike Niggemann, Angew. Chem. Int. Ed. 2010, 49, 3684

  15. Mannich Reaction cat: Kazuaki Ishihara, Angew. Chem. Int. Ed. 2010, 49, 3823

  16. Aliphatic N-Boc imine can react, good yield but low ee Shu Kobayashi, J. Org. Chem. 2010, 75, 963

  17. epoxidation G. Kumaraswamy, Tetrahedron: Asymmetry 14 (2003) 3797

  18. Hydroarylation of Alkenes electrion-rich Aromatic etc Meike Niggemann, Chem. Eur. J. 2010, 16, 11246

  19. Hydroamination Michael S. Hill, J. AM. CHEM. SOC. 2005, 127, 2042

  20. aminoalkene product Time(h) Temp.(oC) Conv.%

  21. Peter W. Roesky, Organometallics 2007, 26, 4392

  22. Pictet-Spengler Reaction regioselective products in most cases, giving rise to only the A-ol isomer. However, when a nitrogen functionality is present, the isomeric ratio of products is altered to give mixtures of the favored 6-ol isomer and the disfavored B-ol regioisomer. such as:

  23. Ketone: James P. Stambuli, ORGANIC LETTERS, 2008, Vol. 10, No. 22, 5289 James P. Stambuli,J. Org. Chem. XXXX, XXX, 000

  24. Tischenko Reaction How to start the catalic cycle? being continuing to study Anthony G. M. Barrett, Michael S. Hill, O. L. 2007, Vol. 9, No. 2, 331

  25. Hydrophosphination Anthony G. M. Barrett, Michael S. Hill, Organometallics 2007, 26, 2953

  26. Anthony G. M. Barrett, Michael S. Hill, Organometallics 2008, 27, 497

  27. Aldol Reaction Ryoji Noyorib, Tetrahedron Letters 42 (2001) 4669

  28. Jieping Zhu, O. L. XXXX, Vol. xx, No. x

  29. strontium Need to develop new ligand

  30. Mannich S. Kobayashi, Angew. Chem. Int. Ed. 2009, 48, 5927 S. Kobayashi ,Bull. Chem. Soc. Jpn. Vol. 82, No. 9, 1083

  31. solvent effect Conditions A: DMF, RT, 17 h, Ar=2,5-xylyl. Conditions B: Ligand 4 (11 mol%), THF, RT, 24 h, Ar=p-NO2-C6H4. The addition of ligand 4 generally increased the syn selectivity

  32. this is the first example of a catalytic asymmetric Mannich-type reaction of a sulfonylimidate

  33. Michael Reactions Ligand: Shuj Kobayashi, J. AM. CHEM. SOC. 2008, 130, 2430

  34. acceptor donor ligand Shu Kobayashi, Chemistry Letters Vol.38, No.3 (2009)

  35. Motomu Kanai, Masakatsu Shibasaki, J. AM. CHEM. SOC. 2010, 132, 8862

  36. barium Barium has the largest ionic radius, which often form oligomer Like:

  37. Diels–Alder-type reaction Motomu Kanai, Angew. Chem. 2009, 121, 1090

  38. Aldol Reaction First example of an optically active alkaline meta catalyst up to 70 ee% Masakatsu Shibasaki, Tetrahedron Letters 39 (1998) 5561

  39. catalytic cycle

  40. Shu Kobayashi, J. AM. CHEM. SOC. 2006, 128, 8704

  41. Masakatsu Shibasaki, J. AM. CHEM. SOC. 2009, 131, 10842

  42. Mannich reaction ligand Shu Kobayashi, Chem. Commun., 2007, 1236

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