71403-94-6

Upstream product

• 106119-54-4 3-hydroxy-5-phenyl-1,2-dioxolane 
• 104-55-2 3-phenyl-propenal 
• 40641-81-4 trans-2,3-epoxy-3-phenylpropan-1-ol 
• 4510-34-3 (Z)-cinnamyl alcohol 
• 104-54-1 3-Phenylpropenol 
• 14371-10-9 (E)-3-phenylpropenal 
• 76777-60-1 5-Hydroxy-5-phenyl-2-<(trimethylsilyl)oxy>-2-methyl-3-pentanone 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 104196-23-8 (2S,3S)-2,3-epoxy-3-phenyl-1-propanol 
• 21915-53-7 cis-2,3-epoxy-3-phenyl-1-propanol 
• 697734-59-1 cinnamylamine 2,3-oxide hydrochloride 
• 99773-42-9 2-Hydroxy-2-methyl-1-((2S,3S)-3-phenyl-oxiranyl)-propan-1-one 
• 21915-53-7 2,3-epoxy-3-phenyl-1-propanol 
• 99773-42-9 2-Hydroxy-2-methyl-1-((2S,3R)-3-phenyl-oxiranyl)-propan-1-one 

Downstream Products

• 91075-30-8 3-Hydroxy-2-methyl-3-(3-phenyl-oxiranyl)-propionic acid methyl ester 
• 128450-34-0 2-((Z)-2-Iodo-vinyl)-3-phenyl-oxirane 
• 128450-34-0 2-((E)-2-Iodo-vinyl)-3-phenyl-oxirane 
• 141191-86-8 (2-Amino-4-butoxy-pteridin-6-yl)-phenyl-methanol 
• 14371-10-9 (E)-3-phenylpropenal 
• 100-52-7 benzaldehyde 
• 20248-57-1 2-phenyl-3-vinyloxirane 
• 15397-33-8 3-Oxo-3-phenylpropanal 
• 950601-14-6 (1R,2R)-3,3-dimethoxy-1-phenylpropane-1,2-diol 
• 36615-45-9 methyl (S)-3-hydroxy-3-phenylpropionate 
• 4660-17-7 rac-6-phenyl-5,6-dihydro-2H-pyran-2-one 
• 115794-66-6 trans-methyl 3-phenylglycidate 
• 115794-67-7 methyl (2R,3S)-3-phenylglycidate 
• 554420-01-8 (+)-(2S,3R)-N-methyl-N-(β-hydroxylphenethyl)-β-phenyl glycidic acid amide 

Relevant academic research and scientific papers

Selective epoxidation of olefins by vanadylporphyrin [V IV O(TPP)] and electron deficient nonplanar β-octabromovanadylporphyrin [V IV O(TPPBr8)]

Meso-tetraphenylporphyrinatooxidovanadium(IV) [VIVO(TPP)] (1) and 2,3,7,8,12,13, 17,18-octabromo-meso-tetraphenylporphyrinatooxidovanadium(IV) [VIVO(TPPBr8)] (2) were synthesized and characterized by various spectroscopic techniques. 1 and 2 were utilized

Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor-Independent Non-natural Peroxygenase

Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and H2O2) to accomplish enantiocomplementary epoxidations of various α,β-unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β-epoxy-aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme-bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor-independent oxidative enzymes.

Palladium-catalysed regio- And stereoselective arylative substitution of γ,δ-epoxy-α,β-unsaturated esters and amides by sodium tetraaryl borates

Palladium-catalysed reactions of γ,δ-epoxy-α,β-unsaturated esters and amides with NaBAr4 reagents proceeded regio- and stereoselectively, producing allylic homoallyl alcohols with aryl-substituents in the allylic position for a wide range of substrates. A

Characteristics and hazards of the cinnamaldehyde oxidation process

Pressure and temperature behavior of the cinnamaldehyde oxidation process was determined using a custom-designed mini closed pressure vessel test (MCPVT), which is a new method to investigate the stability and hazard assesment of the cinnamaldehyde oxidation reaction. The oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that cinnamaldehyde was stable under nitrogen atmosphere but very unstable under oxygen atmosphere. The initial oxidation products were analyzed by iodimetry and the cinnamaldehyde peroxide value could reach 139.44 mmol kg?1when the oxidation temperature was 308 K. The oxidation kinetics of cinnamaldehyde were studied by using the pressureversustime (P-t) curves obtained from the MCPVT process. The reaction is a second-order reaction, the kinetic equation is ln k= ?2233.66 × (1/T) + 11.19, and the activation energyEais 18.57 kJ mol?1at 308-338 K. The explosion of the cinnamaldehyde oxidation reaction was observed by MCPVT, in which the onset temperature was 373 K. The main products of cinnamaldehyde oxidation are acetaldehyde, benzaldehyde, phenylacetaldehyde, acetophenone, 2-hydroxyphenyl acetone, cinnamaldehyde epoxide, benzoic acid, and cinnamic acid. Oxidation is a three-step process: (1) cinnamaldehyde reacts with oxygen to form peroxides; (2) complex oxidation reactions are caused by the thermal decomposition of peroxides; (3) rapid oxidation and thermal decomposition lead to explosion hazard.

Borylation and rearrangement of alkynyloxiranes: A stereospecific route to substituted α-enynes

1,3-Enynes are important building blocks in organic synthesis and also constitute the key motif in various bioactive natural products and functional materials. However, synthetic approaches to stereodefined substituted 1,3-enynes remain a challenge, as they are limited to Wittig and cross-coupling reactions. Herein, stereodefined 1,3-enynes, including tetrasubstituted ones, were straightforwardly synthesized from cis or trans-alkynylated oxiranes in good to excellent yields by a one-pot cascade process. The procedure relies on oxirane deprotonation, borylation and a stereospecific rearrangement of the so-formed alkynyloxiranyl borates. This stereospecific process overall transfers the cis or trans-stereochemistry of the starting alkynyloxiranes to the resulting 1,3-enynes.

Synthesis of Phostones via the Palladium-Catalyzed Ring Opening of Epoxy Vinyl Phosphonates

The reaction of epoxy aldehydes with tetraethyl methylenediphosphonate gave γ,δ-epoxy vinyl phosphonates. The palladium-catalyzed addition of primary alcohols gave the monoprotected diols as single diastereoisomers. The trans- and cis-epoxides lead to opp

Highly Regio- and Stereodivergent Access to 1,2-Amino Alcohols or 1,4-Fluoro Alcohols by NHC-Catalyzed Ring Opening of Epoxy enals

Described is an unprecedented NHC-catalyzed (NHC=N-heterocyclic carbene), stereoselective ring opening of epoxy and cyclopropyl enals to deliver valuable compounds bearing multiple stereocenters. A straightforward three-step procedure involving two catalytic enantioselective transformations has been developed and leads to a regio- and stereodivergent synthesis of either 1,2-amino alcohols/diamines or 1,4-fluoro alcohols with excellent diastereo- and enantiopurity.

Stable Copper Nanoparticle Photocatalysts for Selective Epoxidation of Alkenes with Visible Light

Selective epoxidation of various alkenes with molecular oxygen (O2) under mild conditions is a longstanding challenge in achieving syntheses of epoxides. Cu-based catalysts have been found to be catalytically active for selective epoxidations. However, the application of copper nanoparticles (CuNPs) for photocatalyzed epoxidations is encumbered by the instability of CuNPs in air. Herein we report that CuNPs supported on titanium nitride (TiN) without additional stabilizers not only are stable in air but also can catalyze selective epoxidation of various alkenes with O2 or even air as a benign oxidant under light irradiation. CuNPs remain in the metallic state due to the significant charge transfer that occurs between CuNPs and TiN. The epoxidation is driven by visible light irradiation at moderate temperatures, achieving good to high yields and excellent selectivity. The photocatalytic process is applicable to the selective epoxidation of various alkenes. In this photocatalytic system, reactant alkenes chemically adsorb on CuNPs, forming Cu-alkene surface complexes, and light irradiation can activate the complexes for reaction. The cyclic ether solvent also plays a key role, reacting with O2 on the surface of CuNPs under light irradiation, yielding oxygen adatoms. The activated surface complexes react with the adatoms, yielding the corresponding epoxides. Analysis of the influence of irradiation wavelength and intensity on the epoxidation suggests that light-excited electrons of CuNPs drive the reaction. The adatoms formed react with alkenes, producing the final product epoxides. We also observed interesting product stereoselectivity, predominantly generating the trans isomers for the epoxidation of stilbene (up to 97%). The findings reported here not only provide an effective and selective reaction system for alkene epoxidations but also are a step toward demonstrating the practical use of CuNPs as photocatalysts for various applications.

Nanosheet-enhanced efficiency in amine-catalyzed asymmetric epoxidation of Α, Β-unsaturated aldehydes via host-guest synergy

Amine-catalyzed asymmetric epoxidation of α, β-unsaturated aldehydes has been promoted by attaching the nanosheets of layered double hydroxides (LDHs), a natural and/or synthetic anionic layered compound. 76% of epoxide yield and 93% ee of major diastereomer have been afforded in the asymmetric epoxidation of cinnamaldehyde. The amine sites employed here are the amino group in α-amino acid anion intercalated in the interlayer space of LDHs. The nanosheets of LDHs have been revealed to play key role in the enhancement of catalytic activity by affording the desired basicity and the boost of enantioselectivity by serving as the rigid substituent of amino acids. The hydrophobic interlayer microenvironment and ordered arrangement of intercalated amino acid anions additionally contribute to the catalytic efficacy. Stronger interlayer hydrophobicity favors the conversion and epoxide yield and better arrangement of interlayer anions favors the ee.

Electronic Structure and Multicatalytic Features of Redox-Active Bis(arylimino)acenaphthene (BIAN)-Derived Ruthenium Complexes

The article examines the newly designed and structurally characterized redox-active BIAN-derived [Ru(trpy)(R-BIAN)Cl]ClO4 ([1a]ClO4-[1c]ClO4), [Ru(trpy)(R-BIAN)(H2O)](ClO4)2 ([3a](ClO4)2-[3c](ClO4)2), and BIAO-derived [Ru(trpy)(BIAO)Cl]ClO4 ([2a]ClO4) (trpy = 2,2′:6′,2′′-terpyridine, R-BIAN = bis(arylimino)acenaphthene (R = H (1a+, 3a2+), 4-OMe (1b+, 3b2+), 4-NO2 (1c+, 3c2+), BIAO = [N-(phenyl)imino]acenapthenone). The experimental (X-ray, 1H NMR, spectroelectrochemistry, EPR) and DFT/TD-DFT calculations of 1an-1cn or 2an collectively establish {RuII-BIAN0} or {RuII-BIAO0} configuration in the native state, metal-based oxidation to {RuIII-BIAN0} or {RuIII-BIAO0}, and successive electron uptake processes by the α-diimine fragment, followed by trpy and naphthalene π-system of BIAN or BIAO, respectively. The impact of the electron-withdrawing NO2 function in the BIAN moiety in 1c+ has been reflected in the five nearby reduction steps within the accessible potential limit of -2 V versus SCE, leading to a fully reduced BIAN4- state in [1c]4-. The aqua derivatives ({RuII-OH2}, 3a2+-3c2+) undergo simultaneous 2e-/2H+ transfer to the corresponding {RuIV-O} state and the catalytic current associated with the RuIV/RuV response probably implies its involvement in the electrocatalytic water oxidation. The aqua derivatives (3a2+-3c2+) are efficient and selective precatalysts in transforming a wide variety of alkenes to corresponding epoxides in the presence of PhI(OAc)2 as an oxidant in CH2Cl2 at 298 K as well as oxidation of primary, secondary, and heterocyclic alcohols with a large substrate scope with H2O2 as the stoichiometric oxidant in CH3CN at 343 K. The involvement of the {RuIV-O} intermediate as the active catalyst in both the oxidation processes has been ascertained via a sequence of experimental evidence.