Presentation is loading. Please wait.

Presentation is loading. Please wait.

金属催化的氧化反应 2009.10.17. CYP 450TauD Acc. Chem. Res. 2007, 40, 522–531.

Similar presentations


Presentation on theme: "金属催化的氧化反应 2009.10.17. CYP 450TauD Acc. Chem. Res. 2007, 40, 522–531."— Presentation transcript:

1 金属催化的氧化反应 2009.10.17

2 CYP 450TauD Acc. Chem. Res. 2007, 40, 522–531

3 the first article on the catalytic olefin epoxidation and alkane hydroxylation by a synthetic iron(III) porphyrin complex: Cat: synthetic iron(III) porphyrin complex, Fe(TPP)Cl (TPP=meso-tetraphenylporphyrin) J. Am. Chem. Soc. 1979, 101, 1032–1033.

4 Acc. Chem. Res. 2007, 40, 522–531

5 Ligands that have been used in some Oxygenation Reactions:

6 1. C-H Oxidation A variety of catalysts (including Pt, Pd and Au complexes) and terminal oxidants(such as K2PtCl6, K2S2O8, CuCl2 and O2) have been used. Sen, A. Acc. Chem. Res. 1998, 31, 550–557.

7 The First Catalytic Sulfoxidation of Saturated Hydrocarbons with SO2/O2 by a Vanadium Species: Cat : VO(acac)2 Possible Reaction Path for V-Catalyzed Sulfoxidation:

8 J. Am. Chem. Soc. 2000, 122, 7390-7391 Kalyani, D.; Sanford, M. S. Org. Lett. 2005, 7, 4149–4152.

9 Palladium-Catalyzed Oxygenation of Unactivated sp3 C-H Bonds J. Am. Chem. Soc.2004, 126, 9542–9543. Asymmetric hydroxylation of p-methoxyethylbenzene: ~ 87% ee

10 Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628–3634. Groves, J. T.; Viski, P. J. Am. Chem. Soc. 1989, 111,8537–8538. Tetrahedron 1998, 54, 10017–10028. Chem.Commun. 1999, 1791–1792.

11 Synthesis of 1,3-Difunctionalized Amine Derivatives through Selective C-H Bond Oxidation. J. Am. Chem. Soc. 2001, 123, 6935-6936

12 M. Christina White. J. AM. CHEM. SOC. 2005, 127, 6970-6971

13 Allylic C-H Oxidation/Vinylic C-H Arylation. M. Christina white. J. AM. CHEM. SOC. 2006, 128, 15076-15077

14 J. AM. CHEM. SOC. 2002, 124, 13978-13979

15 The current limitations of this methodology: (i)the general requirement for large excesses of substrate relative to oxidant, (ii) modest levels of chemoselectivity (overoxidation to ketones is a common side reaction), (iii) the general requirement for an activated C-H bond within the molecule, (iv) modest levels of regioselectivity in substrates containing multiple weak C- H bonds, and (v) the inherent difficulties associated with synthesis and modification of porphyrin ligands. Tetrahedron.62 (2006) 2439–2463 Angew. Chem. Int. Ed. 2009, 48, 5720 –5723

16 A Predictably Selective Aliphatic C–H Oxidation Reaction for Complex molecule Synthesis:

17 M. Christina White.science.318,2007,783

18 Stereospecific C-H Oxidation with H 2 O 2 Catalyzed by a chemically Robust Site- Isolated Iron Catalyst

19 The stereospecific hydroxylation of tertiary C-H bonds was also explored, since it opens an entry to trisubstituted chiral alcohols, which is not amenable for free diffusing radical-type reactions. Schematic representation of the ligands used in this study:

20 Xavi Ribas. Angew. Chem. Int. Ed. 2009, 48, 5720 –5723 Chem. Commun., 2007, 4623–4625 Science.312,2006,1941

21 Angew. Chem. Int. Ed. 2009, 48, 3817 –3820 Adv. Synth. Catal. 2007, 349, 865 – 870

22 Eur. J. Org. Chem. 2007, 4654–4657

23 BINOL: A Versatile Chiral Reagent(cr078004a) 75-90 %ee Angew. Chem. Int. Ed. 2003, 42, 6008 –6012

24 2. Dihydroxylation and Epoxidation. For Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide,see Kevin Burgess.Chem. Rev.103,2003,2457.

25 J. Am. Chem. Soc. 2000, 122, 10452-10453 J. Org. Chem. 2009, 74, 3350–3355

26 Angew. Chem. Int. Ed. 2006, 45, 3478

27 Eric N.Jacobsen. J. Am.Chem. Soc.2001,7194

28 9-60% ee Chem. Commun., 2007, 1166–1168

29 Matthias Beller. Angew. Chem. Int. Ed. 2007, 46, 7293 –7296

30 [Fe2O(L)Cl4]: 0-40% ee Chem. Commun., 2008, 3801–3803

31 Iron-Catalyzed Asymmetric Olefin cis-Dihydroxylation with 97% Enantiomeric Excess Lawrence Que, Jr. Angew. Chem. Int. Ed. 2008, 47, 1887 –1889

32 Catalytic Epoxidation and 1,2-Dihydroxylation of Olefins with Bispidine– Iron(ii)/H2O2 Systems pathway A:afford epoxide directly pathway B:be intercepted by O 2 pathway c:be intercepted by Angew. Chem. Int. Ed. 2006, 45, 3446 –3449

33 3. Iron-Catalyzed Asymmetric Sulfide Oxidation J. Legros and C. Bolm, Angew. Chem., Int. Ed., 2004, 43, 4225 PhCH 2 -S-Me:64%yield,23% ee

34 Chem.–Eur. J., 2007, 13, 8045

35 T. Katsuki, J. Am. Chem. Soc., 2007, 129, 8940.

36 Proposed catalytic cycle: Angew. Chem. Int. Ed. 2007, 46, 3718 –3721

37 T. Katsuki.2007 Tsutomu Katsuki.2009


Download ppt "金属催化的氧化反应 2009.10.17. CYP 450TauD Acc. Chem. Res. 2007, 40, 522–531."

Similar presentations


Ads by Google