金属催化的氧化反应

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

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.

Acc. Chem. Res. 2007, 40, 522–531

Ligands that have been used in some Oxygenation Reactions:

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.

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:

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

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

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– Chem.Commun. 1999, 1791–1792.

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

M. Christina White. J. AM. CHEM. SOC. 2005, 127,

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

J. AM. CHEM. SOC. 2002, 124,

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

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

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

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

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:

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

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

Eur. J. Org. Chem. 2007, 4654–4657

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

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

J. Am. Chem. Soc. 2000, 122, J. Org. Chem. 2009, 74, 3350–3355

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

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

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

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

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

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

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

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

Chem.–Eur. J., 2007, 13, 8045

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

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

T. Katsuki.2007 Tsutomu Katsuki.2009