108741-11-3

Upstream product

• 18632-39-8 ethyl 2-hydroxy-3-phenyl-3-oxopropanoate 
• 64-17-5 ethanol 
• 108666-21-3 (3S,5R,6S,9R)-3-((S)-Hydroxy-phenyl-methyl)-9-methyl-6-(1-methyl-1-phenyl-ethyl)-1,4-dioxa-spiro[4.5]decan-2-one 
• 4610-69-9 (Z)-ethyl cinnamate 
• 1118754-99-6 (S)-ethyl 2-diazo-3-hydroxy-3-phenylpropanoate 
• 4192-77-2 ethyl cinnamate 
• 103-36-6 ethyl 3-phenyl-2-propenoate 
• 2272-55-1 ethyl trans-3-phenyl-1-oxirane-2-carboxylate 
• 100-52-7 benzaldehyde 
• 133421-01-9 3-(Dimethylthexylsiloxy)-3-phenyl-2-(trimethylsiloxy)propannitril 
• 5695-95-4 (R)-2,3-Dihydroxy-3-phenyl-propionic acid 

Downstream Products

• 137905-94-3 (2S,3S)-3-Hydroxy-3-phenyl-2-phenylsulfanyl-propionic acid ethyl ester 
• 133520-58-8 [1-((4S,5R)-2,2-Dimethyl-5-phenyl-[1,3]dioxolan-4-yl)-meth-(Z)-ylidene]-((R)-2-methoxymethyl-pyrrolidin-1-yl)-amine 

Relevant academic research and scientific papers

Catalytic Hydroxylation of Olefins by Polymer-Bound Osmium Tetroxide

Osmium tetroxide, linked to insoluble crosslinked polymers and copolymers bearing tertiary amino functions, has been used in the presence of secondary oxidants, such as hydrogen peroxide, tert-butyl hydroperoxide and trimethylamine N-oxide, to accomplish the catalytic hydroxylation of olefins.The polymeric reagent offers the advantages of easy and safe handling, and simple separation from the reaction medium.Generally good yields of vicinal diols have been obtained.

Stereoselective and regioselective reaction of cyclic ortho esters with phenols

Cyclic ortho esters undergo stereoselective and regioselective reaction with phenols when treated with BF3·OEt2 at low temperatures. Attack of the phenol on the ortho ester occurs at an open carbon para to electron-donating groups on the phenol ("C-addition") or at the phenolic hydroxyl group ("O-addition") depending on the nature of the cation formed from reaction of the ortho ester and BF3·OEt2. Products resulting from O-addition undergo reversion to a mixture of starting phenol, C-addition product, and O-addition product if treated with BF3·OEt2 at room temperature, but C-addition products are stable under the same conditions. X-ray structural analysis of the C-addition compound indicates that its stereochemistry is opposite to that observed in reaction of similar ortho esters with chloride from TMSCl. However, the stereochemistry of the reaction can be rationalized by the ability of the ortho ester to isomerize via an intermediate benzylic cation and examination of the preferred trajectory of attack of the nucleophile on the intermediate oxonium ion.

Synthesis and stereochemical assignments for goniobutenolides A and B

Goniobutenolides A and B and their C-7 epimers are stereoselectively synthesized using osmium-catalyzed asymmetric dihydroxylation (AD) as the key transformation. The relative and absolute stereochemistry of the natural goniobutenolides A and B are assigned with reference to the spectral data and optical rotations from the literature.

New polymer supported cinchona alkaloids for heterogeneous catalytic asymmetric dihydroxylation of olefins

Two new polymeric cinchona alkaloid derived ligands were synthesized and utilized in the asymmetric dihydroxylation of olefins, exhibiting high enantioselectivities in the case of aliphatic terminal olefins under heterogeneous phase.

Solvent effect on ruthenium catalyzed dihydroxylation

The effect of different solvents on flash dihydroxylation is compared and for the first time, the replacement of ethyl acetate with acetone was shown to give a successful, catalytic cis-dihydroxylation of the alkene moiety in cholesteryl acetate and the ruthenium catalytic cycle could be maintained by methanesulfonamide in the absence of acetonitrile.

Osmium on chelate resin: Nonvolatile catalyst for the synthesis of DIOLS from alkenes

Osmium tetraoxide (OsO4) was immobilized on a commercially available chelate resin DIAION CR11 (CR11) just by simply immersing it in a methanol solution of OsO4 at room temperature. The resulting purple solid, 5% Os/CR11, indicated no volatility, and effectively catalyzed the oxidation of various alkenes to the corresponding diols.

Synthesis of amino thiols and isocysteines via regioselective ring opening of sulfamidates with tetrathiomolybdate

Herein we present a simple and highly efficient method for the synthesis of β and γ-amino thiols via regioselective ring opening of sulfamidates with tetrathiomolybdate 1. The generality of this methodology has been shown by synthesizing carbohydrate deri

Gelozymes in organic synthesis. Part IV: Resolution of glycidate esters with crude Mung bean (Phaseolus radiatus) epoxide hydrolase immobilized in gelatin matrix

A crude extract of Mung bean meal (Phaseolus radiatus) possessing epoxide hydrolase activity immobilized in gelatin gel (gelozyme) is employed in the stereoselective epoxide ring opening of glycidate esters. Thus, ethyl trans-(±)-3-phenyl glycidate 1a and methyl trans-(±)-3-(4-methoxyphenyl) glycidate 1b gave (2S,3R)-glycidate esters (ee >99% and 45% yield) with gelatin immobilized enzyme in diisopropyl ether. The corresponding (2R,3S)-enantiomer of 1a was hydrolyzed by an epoxide hydrolase to predominantly give the anti-product, ethyl (2R,3R)-2,3-dihydroxy-3-phenylpropanoate, with a diastereomeric excess of 78% and ee 94% (40%). A small amount (5%) of racemic syn-product was also obtained as a result of the spontaneous hydrolysis. In the case of 1b, the hydrolysis product was racemic due to high reactivity of the glycidate toward water.

Alkene cis-dihydroxylation by [(Me3tacn)(CF3CO 2)RuVIO2]CIO4 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane): Structural characterization of [3 + 2] cycloadducts and kinetic studies

cis-Dioxoruthenium(VI) complex [(Me3tacn)(CF3CO 2)RuVIO2]CIO4 (1, Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacted with alkenes in aqueous tert-butyl alcohol to afford cis-1,2-diols in excellent yields under ambient conditions. When the reactions of 1 with alkenes were conducted in acetonitrile, oxidative C=C cleavage reaction prevailed giving carbonyl products in >90% yields without any cis-diol formation. The alkene cis-dihydroxylation and C=C cleavage reactions proceed via the formation of a [3 + 2] cycloadduct between 1 and alkenes, analogous to the related reactions with alkynes [Che et al. J. Am. Chem. Soc. 2000, 122, 11380], With cyclooctene and trans-β-methylstyrene as substrates, the Ru(III) cycloadducts [(Me3tacn)(CF 3CO2)RuIIIO(H)CH(CH2) 6HCO]CIO4 (4a) and [(Me3tacn)(CF 3CO2)RuIIIO(H)-PhCHCH(CH3)O]CIO 4 (4b) were isolated and structurally characterized by X-ray crystal analyses. The kinetics of the reactions of 1 with a series of p-substituted styrenes has been studied in acetonitrile by stopped-flow spectrophotometry. The second-order rate constants varied by 14-fold despite an overall span of 1.3 V for the one-electron oxidation potentials of alkenes. Secondary kinetic isotope effect (KIE) was observed for the oxidation of β-d2-styrene (kH/kD = 0.83 ± 0.04) and α-deuteriostyrene (kH/kD = 0.96 ± 0.03), which, together with the stereoselectivity of cis-alkene oxidation by 1, is in favor of a concerted mechanism.

Ruthenium nanoparticles supported on hydroxyapatite as an efficient and recyclable catalyst for cis-dihydroxylation and oxidative cleavage of alkenes

Impregnation of hydroxyapatite with colloidal ruthenium results in the formation of a catalyst that effects cis-dihydroxylation and oxidative cleavage of alkenes to their respective cis-1,2-diols and carbonyl products in good to excellent yields (see scheme). The supported ruthenium catalyst can be easily recycled and reused for consecutive reaction runs without significant deterioration of the catalytic activities. R1, R2 = H, alkyl, aryl.