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High-Oxidation-State Palladium Catalysis

High-Oxidation-State Palladium Catalysis. 报告人：刘槟. 2010 年 10 月 23 日. Introduction. In 1986 , the first unequivocal trialkylpalladium(IV) complex, [PdIMe 3 (bpy)],was isolated and characterized by X-ray analysis. Acc. Chem. Res . 1992 ,25,83-90. Advantages.

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High-Oxidation-State Palladium Catalysis

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  1. High-Oxidation-State Palladium Catalysis 报告人：刘槟 2010年10月23日

  2. Introduction • In1986 , the first unequivocal trialkylpalladium(IV) complex, [PdIMe3(bpy)],was isolated and characterized by X-ray analysis. Acc. Chem. Res. 1992,25,83-90

  3. Advantages • Some advantages compared to Pd(0)/Pd(II) catalysis: • Pd(IV) species are often resistant to β-H elimination process • Pd(IV) species undergo facile reductive elimination. (like C-C bond formation) • Pd(II)/Pd(IV) catalyzed reactions are operationally simple and do not require the careful exclusion of air (especially O2) and moisture. Chem. Soc. Rev., 2010, 39, 712–733

  4. C-C Coupling Angew. Chem., Int. Ed., 1997, 36, 119

  5. J. AM. CHEM. SOC. 2005, 127, 13148-13149

  6. Chem. Soc. Rev., 2010, 39, 712–733

  7. J. AM. CHEM. SOC. 2006, 128, 4972-4973 Pd0/II versus Proposed PdII/IV Mechanism for Indole Arylation

  8. carbon-carbon bond formation from unactivated alkyl C-H bond J. AM. CHEM. SOC. 2005, 127, 13154-13155

  9. Mechanistic Considerations

  10. J. AM. CHEM. SOC. 2002, 124, 13372-13373

  11. C-O and C-X Bond Formation J. AM. CHEM. SOC. 2004, 126, 2300-2301

  12. J. AM. CHEM. SOC. 2006, 128, 7134-7135

  13. J. AM. CHEM. SOC. 2009, 131, 7520–7521

  14. C-N Bond Formation Proposed Catalytic Cycle J. AM. CHEM. SOC. 2005, 127, 7690-7691

  15. Domino Catalysis Involving Pd(IV) Catalysts J. AM. CHEM. SOC. 2007, 129, 5836-5837

  16. Proposed Mechanism

  17. First example of enantioselective palladium(IV) catalysis J. AM. CHEM. SOC. 2009, 131, 3452–3453

  18. Problems • Little is known about the ligand effect of Pd(IV) complexes • Enantioselective synthesis using chiral ligands through Pd(IV) intermediates has not been forthcoming • Applications to natural product synthesis are lacking • Detailed mechanistic investigation

  19. Conclusion The development of palladium(IV) catalysis has just begun, it has already enabled the development of a number of significant new transformations. These reactions are marked by their high selectivity and synthetic robustness, and almost all are based on the use of catalysts that are generated in situ from commercially available palladium salts.

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