Ruthenium Porphyrin‐Catalyzed Aerobic Oxidation of Terminal Aryl Alkenes to Aldehydes by a Tandem Epoxidation–Isomerization Pathway

Jiang, Gaoxi; Chen, Jian; Thu, Hung‐Yat; Huang, Jie‐Sheng; Zhu, Nianyong; Che, Chi‐Ming

doi:10.1002/anie.200801500

Cited by 107 publications

(47 citation statements)

References 52 publications

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“…Using Ru II (TMP)Cl 2 as a catalyst, Che and co-workers introduced a rare example of olefin epoxidation by dioxygen in base, and the generated epoxide is then in situ isomerized to aldehyde. 16 Examined by 1 H NMR, the reaction was found to have an induction period, followed by dioxoruthenium(VI) intermediate formation through Ru II (TMP)Cl 2 oxidation with dioxygen. Then the in situ generated dioxoruthenium(VI) intermediate initializes the olefin epoxidation.…”

Section: Oxygen Atom Transfer Reactivity Of the Metal Oxo Moietiesmentioning

confidence: 99%

The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations

2015

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While the significance of the redox metal oxo moieties has been fully acknowledged in versatile oxidation processes, active metal hydroxo moieties are gradually realized to play the key roles in certain biological oxidation events, and their reactivity has also been evidenced by related biomimic models. However, compared with the metal oxo moieties, the significance of the metal hydroxo moieties has not been fully recognized, and their relationships in oxidations remain elusive until recently. This review summarizes the reactivity of the metal oxo and hydroxo moieties in different oxidation processes including hydrogen atom transfer, oxygen atom transfer and electron transfer, and their reactivity similarities and differences have been discussed as well. Particularly, how the physicochemical properties like metal-oxygen bond order, net charge and potential of a redox metal ion affect its reactivity has also been presented based on available data. We hope that this review may provide new clues to understand the origins of the enzyme's choice on them in a specific event, to explain the elusive phenomena occurring in those enzymatic, homogeneous and heterogeneous oxidations, to design selective redox catalysts and control their reactivity.

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Section: Oxygen Atom Transfer Reactivity Of the Metal Oxo Moietiesmentioning

confidence: 99%

The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations

2015

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“…150 It is likely that 2-phenylacetaldehyde was formed by over-oxidation of the epoxide, as previously reported with Ru(porphyrins). 152 The nature of the porphyrin had an important effect on the efficiency of the cofactor used. With the cationic Mn III (TMPyP)-estradiol, the conversion of styrene was almost quantitative, whereas much lower yields were observed with the anionic Mn III (TpSPP)-estradiol.…”

Section: Catalytic Activity Of the Metalloporphyrin-estradiol-7a3mentioning

confidence: 99%

From “hemoabzymes” to “hemozymes”: towards new biocatalysts for selective oxidations

2015

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The design of artificial hemoproteins that could catalyze selective oxidations using clean oxidants such as O2 or H2O2 under ecocompatible conditions constitutes a real challenge for a wide range of industrial applications. In vivo, such reactions are performed by heme-thiolate proteins, cytochromes P450, which catalyze the oxidation of substrates by dioxygen in the presence of electrons delivered from NADPH by cytochrome P450 reductase. Several strategies were used to design new artificial hemoproteins that mimic these enzymes. The first one involved the non-covalent association of synthetic hemes with monoclonal antibodies raised against these cofactors. This led to the first generation of artificial hemoproteins or "hemoabzymes" that displayed a peroxidase activity, and in some cases catalyzed the regioselective nitration of phenols by H2O2/NO2 and the stereoselective oxidation of sulfides by H2O2. The second one involved the non-covalent association of easily affordable non-relevant proteins with metalloporphyrin derivatives, using either the "Trojan Horse strategy" or the "host-guest" strategy. This led to a second generation of artificial hemoproteins or "hemozymes", some of which were found able to catalyze the stereoselective oxidation of organic compounds such as sulfides and alkenes by H2O2 and KHSO5.

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“…37,41a,45 We have also prepared [Ru II (F 28 -tpp)(CO)] by the reaction of H 2 (F 28 -tpp) with Ru 3 (CO) 12 in 1,2,4-trichlorobenzene; 45 , which bears a bis-pocket porphyrin, is a robust catalyst for the aerobic oxidation of alkenes. 43 To facilitate catalyst recycling and improve selectivity, we prepared heterogenized ruthenium porphyrin catalysts [Ru II (por)(CO)]-MCM-41 (por = 4-Cl-tpp, 46 2,6-Cl 2 tpp, 47 D 4 -por* 48 ) and [Ru II (D 4 -por*)(CO)]-MCM-48 48 by grafting the corresponding [Ru II (por)(CO)] onto the surface-modified mesoporous molecular sieves (MCM-41 or -48) through coordination bonds (Fig. 4).…”

Section: Catalyst Developmentmentioning

confidence: 99%

“…63b,c We have developed metalloporphyrin-based oxidation systems that efficiently oxidize a series of 1-alkenes to aldehydes. 37,43 By using the oxidation systems M, N, S, T and V (Table 1), consisting of ruthenium porphyrin catalysts and terminal oxidants 2,6-Cl 2 pyNO or O 2 , the alkenes 31a-h and 33a-f,k-m,o,q, together with 1a-c,e,k,t used in the epoxidation reactions, have been converted to the corresponding aldehydes in good to high yields. The aldehyde products 32a-h and 34a-q, along with the highest yields and the oxidation systems employed, are shown in Scheme 10.…”

Section: Oxidation Of 1-alkenes To Aldehydesmentioning

confidence: 99%

Metalloporphyrin-based oxidation systems: from biomimetic reactions to application in organic synthesis

2009

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The oxidation of organic substrates catalyzed by metalloporphyrins constitutes a major class of biomimetic oxidation reactions used in modern synthetic chemistry. Ruthenium porphyrins are among the most extensively studied metalloporphyrin oxidation catalysts. This article provides a brief outline of the metalloporphyrin-based oxidation systems and is focused on the oxidation reactions catalyzed by ruthenium porphyrins performed in the author's laboratory. A series of ruthenium porphyrin catalysts, including those immobilized onto insoluble supports and covalently attached to soluble supports, promote the oxidation of a wide variety of organic substrates such as styrenes, cycloalkenes, alpha,beta-unsaturated ketones, steroids, benzylic hydrocarbons and arenes with 2,6-dichloropyridine-N-oxide or air in up to >99% yields, with high regio-, chemo- and/or stereoselectivity, and with product turnovers of up to 3.0x10(4), demonstrating the potential application of ruthenium porphyrin-based oxidation systems in organic syntheses.

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Ruthenium Porphyrin‐Catalyzed Aerobic Oxidation of Terminal Aryl Alkenes to Aldehydes by a Tandem Epoxidation–Isomerization Pathway

Cited by 107 publications

References 52 publications

The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations

The reactivity of the active metal oxo and hydroxo intermediates and their implications in oxidations

From “hemoabzymes” to “hemozymes”: towards new biocatalysts for selective oxidations

Metalloporphyrin-based oxidation systems: from biomimetic reactions to application in organic synthesis

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