13595-05-6

Upstream product

• 766-90-5 cis-1-phenyl-1-propylene 
• 14222-20-9 1R,2R-N-methylpseudoephedrine 
• 1201-56-5 (1S,2S)-N-Methylpseudoephedrine 
• 4541-87-1 cis-1-phenylpropene oxide 
• 873-66-5 1-propenylbenzene 
• 95-20-5 2-methyl-1H-indole 
• 637-50-3 1-phenylpropene 
• 4773-35-7 1-chloro-1-phenylpropan-2-one 
• 93-55-0 1-phenyl-propan-1-one 
• 103-79-7 1-phenyl-acetone 
• 4180-23-8 E-1-(4'-methoxyphenyl)prop-1-ene 
• 6084-17-9 2-chloro-1-phenylpropan-1-one 
• 160332-15-0 (+)-(1S,2S)-1-phenyl-1-chloro-2-propanol 
• 160332-19-4 (-)-(1R,2R)-1-phenyl-2-chloro-1-propanol 

Downstream Products

• 39615-80-0 d,l-1-phenyl-2-methyl-4-penten-2-ol 
• 74333-46-3 anti-2-phenyl-5-hexen-3-ol 
• 74333-47-4 phenyl-2 hexene-5 ol-3 
• 120318-52-7 3-phenylhex-5-en-3-ol 
• 698-87-3 3-phenyl-2-propanol 

Relevant academic research and scientific papers

Aerobic enantioselective alkene epoxidation by a chiral trans-dioxo(D4-porphyrinato)ruthenium(VI) complex

A dioxoruthenium(VI) complex with a D4-chiral porphyrin ligand has been prepared and characterized by spectroscopic methods and X-ray crystal analysis; the complex exhibits catalytic activity towards aerobic enantioselective epoxidation of proc

Asymmetric Epoxidation of Olefins Catalyzed by Substituted Aminobenzimidazole Manganese Complexes Derived from L-Proline

A family of manganese complexes [Mn(Rpeb)(OTf)2] (peb=1-(1-ethyl-1H-benzo[d]imidazol-2-yl)-N-((1-((1-ethyl-1H-benzo[d]imidazol-2-yl)methyl) pyrrolidin-2-yl)methyl)-N-methylmethanamine)) derived from L-proline has been synthesized and characterized, where R refers to the group at the diamine backbone. X-ray crystallographic analyses indicate that all the manganese complexes [Mn(Rpeb)(OTf)2] exhibit cis-α topology. These types of complexes are shown to catalyze the asymmetric epoxidation of olefins employing H2O2 as a terminal oxidant with up to 96% ee. Obviously, the R group of the diamine backbone can influence the catalytic activity and enantioselectivity in the asymmetric epoxidation of olefins. In particular, Mn(i-Prpeb)(OTf)2 bearing an isopropyl arm, cannot catalyze the epoxidation reaction with H2O2 as the oxidant. However, when PhI(OAc)2 is used as the oxidant instead, all the manganese complexes including Mn(i-Prpeb)(OTf)2 can promote the epoxidation reactions efficiently. Taken together, these results indicate that isopropyl substitution on the Rpeb ligand inhibits the formation of active Mn(V)-oxo species in the H2O2/carboxylic acid system via an acid-assisted pathway.

Enantioselective, Stereoconvergent Resolution Copolymerization of Racemic cis-Internal Epoxides and Anhydrides

Unprecedented enantioselective resolution copolymerization of racemic cis-internal epoxides and anhydrides was mediated by dinuclear aluminum complexes with multiple chirality, affording optically active polyesters with two contiguous stereogenic centers, and the unreacted substrates in good enantioselectivity. Unexpected stereoconvergence is observed in this resolution copolymerization, where the selectivity factor for the enantioselective formation of copolymer significantly exceeds the kinetic resolution coefficient based on the unreacted epoxide at various conversions. Catalytic activity and copolymer enantioselectivity are strongly influenced by the phenolate ortho-substituents of the ligand set, as well as the axial linker and its chirality. An enantiopure binaphthol-linked bimetallic AlIII complex allows stereoconvergent access to the stereoregular semi-crystalline polyesters and a concomitant kinetic resolution of the epoxide substrates.

Chiral Manganese Aminopyridine Complexes: the Versatile Catalysts of Chemo- and Stereoselective Oxidations with H2O2

In the last decade, manganese(II) complexes with N-donor tetradentate aminopyridine ligands emerged as efficient catalysts of enantioselective epoxidation of olefins and direct selective oxidation of C?H groups in complex organic molecules, with environmentally benign oxidant hydrogen peroxide. In this personal account, we summarize the progress of these catalysts with regard to ligands design, structure-reactivity correlations, evaluation of the substrate scope, as well as mechanistic studies, shedding light on the nature of active sites and the mechanisms of selective oxygenations. Several practically promising catalytic syntheses with the aid of Mn aminopyridine catalysts are exemplified.

Enhanced Turnover for the P450 119 Peroxygenase-Catalyzed Asymmetric Epoxidation of Styrenes by Random Mutagenesis

A randomized library is constructed based on pET30a-CYP119-T214V plasmid. This library of random mutants of CYP119-T214V was screened by means of the reduced CO difference spectra and epoxidation of styrene. By using directed evolution, a new CYP119 quadr

Asymmetric Epoxidation of Olefins with H2O2 Catalyzed by a Bioinspired Aminopyridine N4 Iron Complex

An iron complex with a chiral aminopyridine N4 ligand bearing strong electron-donating and bulky morpholine groups on the ligand is synthesized and characterized. The iron complex serves to efficiently catalyze the asymmetric epoxidation of various olefins by employing aqueous hydrogen peroxide as the green oxidant, providing the corresponding epoxides in good to excellent yields and enantioselectivities (up to 93 % yield and 99.9 % ee). Owing to the introduction of morpholine functional groups on the ligand, the Fe-catalyzed reaction can proceed with a catalytic amount of the carboxylic acid partner (3 mol %).

Photocatalytic Asymmetric Epoxidation of Terminal Olefins Using Water as an Oxygen Source in the Presence of a Mononuclear Non-Heme Chiral Manganese Complex

Photocatalytic enantioselective epoxidation of terminal olefins using a mononuclear non-heme chiral manganese catalyst, [(R,R-BQCN)MnII]2+, and water as an oxygen source yields epoxides with relatively high enantioselectivities (e.g., up to 60% enantiomeric excess). A synthetic mononuclear non-heme chiral Mn(IV)-oxo complex, [(R,R-BQCN)MnIV(O)]2+, affords similar enantioselectivities in the epoxidation of terminal olefins under stoichiometric reaction conditions. Mechanistic details of each individual step of the photoinduced catalysis, including formation of the Mn(IV)-oxo intermediate, are discussed on the basis of combined results of laser flash photolysis and other spectroscopic methods.

Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts

We report a remarkable Br?nsted acid effect in the epoxidation of olefins by nonheme manganese catalysts and aqueous hydrogen peroxide. More specifically, a mononuclear nonheme manganese complex bearing a tetradentate N4 ligand, MnII(Dbp-MCP)(OTf)2 (Dbp-MCP = (1R,2R)-N,N′-dimethyl-N,N′-bis((R)-(3,5-di-tert-butyl-phenyl)-2-pyridinylmethyl)cyclohexane-1,2-diamine; OTf- = CF3SO3-), is a highly efficient catalyst in the epoxidation of olefins by aqueous H2O2 in the presence of H2SO4 (1-3 mol %). The yields of epoxide products as well as the chemo- and enantioselectivities increase dramatically in the presence of H2SO4; no formation of epoxides is observed in the absence of H2SO4. In addition, the product yields and enantioselectivities are dependent significantly on the manganese catalysts and Br?nsted acids. The catalytic epoxidation of olefins by other oxidants, such as peracids, alkyl hydroperoxides, and iodosylbenzene, is also affected by the presence of H2SO4; product yields and enantioselectivities are high and similar irrespective of the oxidants in the presence of H2SO4, suggesting that a common epoxidizing intermediate is generated in the reactions of [MnII(Dbp-MCP)]2+ and the oxidants. Mechanistic studies, performed with 18O-labeled water (H218O) and cumyl hydroperoxide, reveal that a high-valent manganese-oxo species is formed as an epoxidizing intermediate via O-O bond heterolysis of Mn-OOH(R) species. The role of H2SO4 is proposed to facilitate the formation of a high-valent Mn-oxo species and to increase the oxidizing power and enantioselectivity of the Mn-oxo oxidant in olefin epoxidation reactions. Density functional theory (DFT) calculations support experimental results such as the formation of a Mn(V)-oxo species as an epoxidizing intermediate.

Ti-salalen mediated asymmetric epoxidation of olefins with H2O2: Effect of ligand on the catalytic performance, and insight into the oxidation mechanism

The highly enantioselective epoxidation of several conjugated olefins with H2O2 in the presence of five chiral titanium(IV) salalen (dihydrosalen) complexes has been studied, with focus on the effects of substituents (electronic and

Engineering P450 Peroxygenase to Catalyze Highly Enantioselective Epoxidation of cis-β-Methylstyrenes

P450 119 peroxygenase and its site-directed mutants are discovered to catalyze the enantioselective epoxidation of methyl-substituted styrenes. Two new site-directed P450 119 mutants, namely T213Y and T213M, which were designed to improve the enantioselectivity and activity for the epoxidation of styrene and its methyl substituted derivatives, were studied. The T213M mutant is found to be the first engineered P450 peroxygenase that shows highly enantioselective epoxidation of cis-β-methylstyrenes, with up to 91 % ee. Molecular modeling studies provide insights into the different catalytic activity of the T213M mutant and the T213Y mutant in the epoxidation of cis-β-methylstyrene. The results of the calculations also contribute to a better understanding of the substrate specificity and configuration control for the regio- and stereoselective peroxygenation catalyzed by the T213M mutant.