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

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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.

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

CYP 450TauD Acc. Chem. Res. 2007, 40, 522531 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, 10321033. Acc. Chem. Res. 2007, 40, 522531 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, 550557. 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, 41494152. Palladium-Catalyzed Oxygenation of Unactivated sp3 C-H Bonds J. Am. Chem. Soc.2004, 126, 95429543. Asymmetric hydroxylation of p-methoxyethylbenzene: ~ 87% ee Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 36283634. Groves, J. T.; Viski, P. J. Am. Chem. Soc. 1989, 111,85378538. Tetrahedron 1998, 54, 10017 Chem.Commun. 1999, 17911792. 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) 24392463 Angew. Chem. Int. Ed. 2009, 48, 5720 5723 A Predictably Selective Aliphatic CH 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, 46234625 Science.312,2006,1941 Angew. Chem. Int. Ed. 2009, 48, 3817 3820 Adv. Synth. Catal. 2007, 349, 865 870 Eur. J. Org. Chem. 2007, 46544657 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, 33503355 Angew. Chem. Int. Ed. 2006, 45, 3478 Eric N.Jacobsen. J. Am.Chem. Soc.2001,7194 9-60% ee Chem. Commun., 2007, 11661168 Matthias Beller. Angew. Chem. Int. Ed. 2007, 46, 7293 7296 [Fe2O(L)Cl4]: 0-40% ee Chem. Commun., 2008, 38013803 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