1689-70-9

Upstream product

• 592-99-4 4-octene 
• 14850-23-8 trans-4-Octene 
• 632-21-3 1,1,3,3-tetrachloropropanone 
• 60221-14-9 erythro-5-(Phenylseleno)octan-4-ol 
• 75250-50-9 erythro-5-hydroxy-4-octyl phenyl telluride 
• 75-91-2 tert.-butylhydroperoxide 
• 7642-15-1 (Z)-oct-4-ene 
• 108-24-7 acetic anhydride 

Downstream Products

• 18295-59-5 2-propylpentanal 
• 2616-99-1 trans-Oct-3-en-5-ol 
• 71098-70-9 (4R*,5S*)-5-phenylthio-4-octanol 
• 75250-50-9 5-hydroxyoctan-4-yl phenyl telluride 
• 14850-23-8 trans-4-Octene 
• 84988-12-5 <4-(5-hydroxyoctyl)>phenyltellurium dibromide 
• 589-62-8 octan-4-ol 
• 59734-23-5 trans-5-methyloct-4-ol 

Relevant academic research and scientific papers

A Self-Assembled Molecular Cage for Substrate-Selective Epoxidation Reactions in Aqueous Media

Encapsulation of a manganese porphyrin in a self-assembled molecular cage allows catalytic epoxidation of various substrates in 1:1 water/acetonitrile mixtures. The cage acts as a phase-transfer catalyst and creates a protective environment for the catalyst improving the stability. The encapsulated catalyst also allows discrimination between styrene derivatives of various sizes. In a direct competition experiment, the selectivity of the epoxidation reaction could be inverted with respect to a benchmark catalyst.

Making Fe(BPBP)-catalyzed C-H and CC oxidations more affordable

The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α- [Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf) 2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C-H and C=C bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C-H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude dl/meso-2,2′-bipyrrolidine. Next to its use in C-H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.

Cyclopropenone catalyzed substitution of alcohols with mesylate ion

The cyclopropenone catalyzed nucleophilic substitution of alcohols by methanesulfonate ion with inversion of configuration is described. This work provides an alternative to the Mitsunobu reaction that avoids the use of azodicarboxylates and generation of hydrazine and phosphine oxide byproducts. This transformation is shown to be compatible with a range of functionality. A cyclopropenone scavenge strategy is demonstrated to aid purification.

Epoxidation of olefins by β-bromoalkoxydimethylsulfonium ylides

Olefins can be converted to their respective epoxides in a one-pot procedure by dissolving the olefin in anhydrous DMSO, adding NBS to the reaction mixture to generate a β-bromoalkoxydimethylsulfonium ylide, and then adding DBU to the reaction mixture. A large variety of alkenes were successfully epoxi-dized with yields largely dependent on the structure of the alkene. Most importantly, the facial selectivity of this one-pot process is the opposite of that observed when using traditional epoxidizing reagents. Electron-poor alkenes are not epoxidized under these conditions.

Synthesis, crystal structure, and catalytic properties of novel dioxidomolybdenum(VI) complexes with tridentate schiff base ligands in the biomimetic and highly selective oxygenation of alkenes and sulfides

Four novel dioxidomolybdenum(VI) complexes [MoO2(L x)(CH3OH)] have been synthesized, using 2[(E)-(2-hydroxy-2-phenylethylimino)methyl]phenol derivatives as tridentate ONO donor Schiff base ligands (H2Lx) and MoO 2(acac)2. A monoclinic space group was determined by X-ray crystallography from single-crystal data of a sample of these new complexes. The epoxidation of alkenes by using tert-butyl hydroperoxide and oxidation of sulfides to sulfoxides by urea hydrogen peroxide were efficiently enhanced with excellent selectivity under the catalytic influence these new MoVI complexes. The high efficiency and relative stability of the catalysts have been observed, by turnover numbers and UV/Vis investigations. The electron-poor and bulky ligands promoted the effectiveness of the catalysts. 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Olefin-dependent discrimination between two nonheme HO-Fev=O tautomeric species in catalytic H2O2 epoxidations

A study was conducted to demonstrate olefin-dependent discrimination of two nonheme HO-Fev=O tautomeric species in catalytic H2O 2 epoxidations. Mechanistic studies were carried out under the condition of excess of olefin to minimize over-oxidation reactions and all reactions for the study were carried out under a N2 atmosphere to prevent auto-oxidation process due to presence of O2. It was observed that the diol/epoxide (D/E) ration for these reaction was dependent on the specific olefin and ranged from 3/2 (cyclooctene) to 6/1 (1-octene). The oxidation of cyclooctene using H218O2 revealed that only 28% of the oxygen atoms in the epoxide derived from H 2O2. Mechanistic results suggested that HO-Fe v=O oxidant need to be labeled before its reaction with substrates.

Efficient and selective peracetic acid epoxidation catalyzed by a robust manganese catalyst

(Chemical Equation Presented) A manganese catalyst containing a tetradentate ligand derived from triazacyclononane exhibits high catalytic activity in epoxidation reactions using peracetic acid as oxidant. The system exhibits broad substrate scope and requires small (0.1-0.15 mol %) catalyst loading. The catalyst is remarkably selective toward aliphatic cis-olefins. Mechanistic studies point toward an electrophilic oxidant delivering the oxygen atom in a concerted step.

Non-heme iron complexes for stereoselective oxidation: Tuning of the selectivity in dihydroxylation using different solvents

A new class of functional models for non-heme iron-based dioxygenases, including [(N3Py-Me)Fe(CH3CN)2](ClO4) 2 and [(N3Py-Bn)Fe(CH3CN)2](ClO 4)2 {N3Py-Me = [di(2-pyridyl)methyl]methyl(2-pyridyl) methylamine; N3Py-Bn = [di(2-pyridyl)methyl]benzyl(2-pyridyl)methylamine}, is presented here. NMR, UV and X-ray analyses revealed that six-coordinate low-spin FeII complexes with the pyridine N-atoms and the tertiary amine functionality of the ligand bound to Fe are formed. The two remaining coordination sites located cis to each other are occupied by labile CH 3CN groups that are easily exchanged by other ligands. We demonstrate that the reactivity and stereoselectivity of the complexes investigated depend on the choice of the solvent. The complexes have been examined as catalysts for the oxidation of both alkanes and olefins in CH3CN. In this solvent alkanes are oxidized to alcohols and ketones and olefins to the corresponding cis-epoxides and cis-diols. In acetone as solvent a different reactivity pattern was found, with, as the most striking example, the trans-dihydroxylation of cis-olefins. 18O-labeling studies in CH3CN establish incorporation of 18O from H218O2 and H218O in both the epoxide and the diol implicating an HO-FeV=18O active intermediate originating from an H 218O-FeIIIOOH species. These results are in full agreement with mechanistic schemes derived for other dioxygenase model systems. Based on labeling studies in acetone an additional oxidation mechanism is proposed for this solvent, in which the solvent acetone is involved. This is the first example of a catalyst that can give cis- or trans-dihydroxylation products, just by changing the solvent. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Polyfluorinated quaternary ammonium salts of polyoxometalate anions: Fluorous biphasic oxidation catalysis with and without fluorous solvents

[Matrix presented] Polyfluorinated quaternary ammonium cations, [CF 3(CF2)7(CH2)3] 3CH3N+ (RFN+), were synthesized and used as countercations for the [WZnM2(H 2O)2(ZnW9O34)2] 12- (M = Mn(II), Zn(II)) polyoxometalate. The (RFN +)12[WZnM2(H20)2 (ZnW9O34)2] compounds were fluorous biphasic catalysts for alcohol and alkenol oxidation, and alkene epoxidation with aqueous hydrogen peroxide. Reaction protocols with or without a fluorous solvent were tested. The catalytic activity and selectivity was affected by both the hydrophobicity of the solvent and the substrate.

Manganese-catalyzed epoxidations of alkenes in bicarbonate solutions

This paper describes a method, discovered and refined by parallel screening, for the epoxidation of alkenes. It uses hydrogen peroxide as the terminal oxidant, is promoted by catalytic amounts (1.0-0.1 mol %) of manganese(2+) salts, and must be performed using at least catalytic amounts of bicarbonate buffer. Peroxymonocarbonate, HCO4-, forms in the reaction, but without manganese, minimal epoxidation activity is observed in the solvents used for this research, that is, DMF and tBUOH. More than 30 d-block and f-block transition metal salts were screened for epoxidation activity under similar conditions, but the best catalyst found was MnSO4. EPR studies show that Mn2+ is initially consumed in the catalytic reaction but is regenerated toward the end of the process when presumably the hydrogen peroxide is spent. A variety of aryl-substituted, cyclic, and trialkyl-substituted alkenes were epoxidized under these conditions using 10 equiv of hydrogen peroxide, but monoalkyl-alkenes were not. To improve the substrate scope, and to increase the efficiency of hydrogen peroxide consumption, 68 diverse compounds were screened to find additives that would enhance the rate of the epoxidation reaction relative to a competing disproportionation of hydrogen peroxide. Successful additives were 6 mol % sodium acetate in the tBUOH system and 4 mol % salicylic acid in the DMF system. These additives enhanced the rate of the desired epoxidation reaction by 2-3 times. Reactions performed in the presence of these additives require less hydrogen peroxide and shorter reaction times, and they enhance the yields obtained from less reactive alkene substrates. Possible mechanisms for the reaction are discussed.