148684-05-3

Upstream product

• 2039-82-9 1-bromo-4-ethenyl-benzene 
• 32017-76-8 (+/-)-2-(4-bromophenyl)oxirane 
• 306282-42-8 (S)-2-(4-bromophenyl)-2-hydroxyethyl 4-methylbenzenesulfonate 
• 4248-19-5 tert-butyl carbazate 
• 99-90-1 para-bromoacetophenone 
• 98475-05-9 α-tosyloxy-4-bromoacetophenone 
• 117465-34-6 2-bromo-1-(4-bromophenyl)ethanol 
• 117340-82-6 (S)-1-acetoxy-2-bromo-1-(4-bromophenyl)ethane 
• 65-85-0 benzoic acid 
• 1122-91-4 4-bromo-benzaldehyde 
• 1030268-21-3 trimethylsulfonium iodide 
• 99-73-0 para-bromophenacyl bromide 
• 1186072-12-7 [(2R,3S)-3-(4-bromophenyl)oxiran-2-yl]trimethylsilane 
• 92093-23-7 1-(4-bromophenyl)ethane-1,2-diol 

Downstream Products

• 201403-14-7 (S)-N²-[2-Hydroxy-1-(p-bromophenyl)ethyl]guanosine 
• 877876-61-4 (R)-3-(4'-bromophenyl)-3-hydroxypropanenitrile 
• 879205-72-8 (1S)-1-(4-bromophenyl)-2-((1R)-1-phenylethylamino)-ethanol 
• 1304788-20-2 C₁₄H₁₃BrO₂ 
• 92093-23-7 (R)-(-)-1-(4-bromophenyl)-1,2-ethanediol 
• 73918-56-6 4-Bromophenethylamine 
• 27200-79-9 p-bromophenylacetaldehyde 
• 849178-85-4 tert-butyl N-[(1R)-1-(4-bromophenyl)-2-hydroxy-ethyl]carbamate 
• 354153-64-3 (R)-2-amino-2-(4-bromophenyl)ethan-1-ol 
• 1323142-77-3 (S)-(+)-1-adamantylamino-2-[4-(4-chlorophenylthio)phenyl]propan-2-ol 
• 1323142-73-9 (S)-(+)-4-(4-chlorophenylthio)styrene oxide 
• 160332-70-7 (S)-(+)-1-(4-bromophenyl)-1,2-ethanediol 

Relevant academic research and scientific papers

Synthesis of new chiral Mn(iii)-salen complexes as recoverable and reusable homogeneous catalysts for the asymmetric epoxidation of styrenes and chromenes

New chiral Mn(iii)-salen complexes 1a-e and 2a-e were synthesized from the reaction of C2-symmetric chiral salen ligands and Mn(CH3COO)2·4H2O under an inert atmosphere followed by aerobic oxidation. These complexes were obtained in 91-96% yields and characterized by HRMS, FT-IR, UV-visible spectroscopy, TGA, and elemental analysis. The chiral Mn(iii)-salen complexes 1a-e and 2a-e were evaluated in the asymmetric epoxidation of styrene using NaOCl as an oxidant in ethyl acetate as a green solvent. The chiral Mn(iii)-salen complexes 1b and 2b (2 mol%) catalyzed the asymmetric epoxidation of substituted styrenes and chromenes to afford the corresponding epoxides in 95-98% yields with 29-88% ee's. The catalysts 1b and 2b were recovered and reused for up to 2 and 3 runs, respectively, in the asymmetric epoxidation of styrene, and the yield of styrene oxide gradually decreased but the ee was consistent.

Structure-Guided Regulation in the Enantioselectivity of an Epoxide Hydrolase to Produce Enantiomeric Monosubstituted Epoxides and Vicinal Diols via Kinetic Resolution

Structure-guided microtuning of an Aspergillus usamii epoxide hydrolase was executed. One mutant, A214C/A250I, displayed a 12.6-fold enhanced enantiomeric ratio (E = 202) toward rac-styrene oxide, achieving its nearly perfect kinetic resolution at 0.8 M in pure water or 1.6 M in n-hexanol/water. Several other beneficial mutants also displayed significantly improved E values, offering promising biocatalysts to access 19 structurally diverse chiral monosubstituted epoxides (97.1 - ≥ 99% ees) and vicinal diols (56.2-98.0% eep) with high yields.

Diastereoselective Alkene Hydroesterification Enabling the Synthesis of Chiral Fused Bicyclic Lactones

Palladium-catalysed diastereoselective hydroesterification of alkenes assisted by the coordinative hydroxyl group in the substrate afforded a variety of chiral γ-butyrolactones bearing two stereocenters. Employing the carbonylation-lactonization products as the key intermediates, the route from the alkenes with single chiral center to chiral THF-fused bicyclic γ-lactones containing three stereocenters was developed.

The Stereoselective Oxidation of para-Substituted Benzenes by a Cytochrome P450 Biocatalyst

The serine 244 to aspartate (S244D) variant of the cytochrome P450 enzyme CYP199A4 was used to expand its substrate range beyond benzoic acids. Substrates, in which the carboxylate group of the benzoic acid moiety is replaced were oxidised with high activity by the S244D mutant (product formation rates >60 nmol.(nmol-CYP)?1.min?1) and with total turnover numbers of up to 20,000. Ethyl α-hydroxylation was more rapid than methyl oxidation, styrene epoxidation and S-oxidation. The S244D mutant catalysed the ethyl hydroxylation, epoxidation and sulfoxidation reactions with an excess of one stereoisomer (in some instances up to >98 %). The crystal structure of 4-methoxybenzoic acid-bound CYP199A4 S244D showed that the active site architecture and the substrate orientation were similar to that of the WT enzyme. Overall, this work demonstrates that CYP199A4 can catalyse the stereoselective hydroxylation, epoxidation or sulfoxidation of substituted benzene substrates under mild conditions resulting in more sustainable transformations using this heme monooxygenase enzyme.

A new clade of styrene monooxygenases for (R)-selective epoxidation

Styrene monooxygenases (SMOs) are excellent enzymes for the production of (S)-enantiopure epoxides, but so far, only one (R)-selective SMO has been identified with a narrow substrate spectrum. Mining the NCBI non-redundant protein sequences returned a new distinct clade of (R)-selective SMOs. Among them,SeStyA fromStreptomyces exfoliatus,AaStyA fromAmycolatopsis albispora, andPbStyA fromPseudonocardiaceaewere carefully characterized and found to convert a spectrum of styrene analogues into the corresponding (R)-epoxides with up to >99% ee. Moreover, site 46 (AaStyA numbering) was identified as a critical residue that affects the enantioselectivity of SMOs. Phenylalanine at site 46 was required for the (R)-selective SMO to endow excellent enantioselectivity. The identification of new (R)-selective SMOs would add a valuable green alternative to the synthetic tool box for the synthesis of enantiopure (R)-epoxides.

Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade

Enantioenriched azido alcohols are precursors for valuable chiral aziridines and 1,2-amino alcohols, however their chiral substituted analogues are difficult to access. We established a cascade for the asymmetric azidohydroxylation of styrene derivatives leading to chiral substituted 1,2-azido alcohols via enzymatic asymmetric epoxidation, followed by regioselective azidolysis, affording the azido alcohols with up to two contiguous stereogenic centers. A newly isolated two-component flavoprotein styrene monooxygenase StyA proved to be highly selective for epoxidation with a nicotinamide coenzyme biomimetic as a practical reductant. Coupled with azide as a nucleophile for regioselective ring opening, this chemo-enzymatic cascade produced highly enantioenriched aromatic α-azido alcohols with up to >99% conversion. A bi-enzymatic counterpart with halohydrin dehalogenase-catalyzed azidolysis afforded the alternative β-azido alcohol isomers with up to 94% diastereomeric excess. We anticipate our biocatalytic cascade to be a starting point for more practical production of these chiral compounds with two-component flavoprotein monooxygenases.

Peroxygenase-Catalysed Epoxidation of Styrene Derivatives in Neat Reaction Media

Biocatalytic oxyfunctionalisation reactions are traditionally conducted in aqueous media limiting their production yield. Here we report the application of a peroxygenase in neat reaction conditions reaching product concentrations of up to 360 mM.

Photoenzymatic epoxidation of styrenes

Two-component-diffusible-flavomonooxygenases are versatile biocatalysts for selective epoxidation-, hydroxylation- or halogenation reactions. Their complicated molecular architecture can be simplified using photochemical regeneration of the catalytically

Immobilization of Amano lipase from Pseudomonas fluorescens on silk fibroin spheres: an alternative protocol for the enantioselective synthesis of halohydrins

The search for a new, efficient, cheaper and sustainable matrix for lipase immobilization is a growing area in biotechnology. Amano lipase from Pseudomonas fluorescens was immobilized on silk fibroin spheres and used in the enzymatic kinetic resolution of halohydrins, to obtain optically active epoxides (up to 99% ee), important precursors in the synthesis of derivative antifungal azoles. This paper reinforces the versatility of silk fibroin as a support for heterogeneous catalysts.

Highly Enantioselective Hydrosilylation of Ketones Catalyzed by a Chiral Oxazaborolidinium Ion

A highly enantioselective hydrosilylation of ketones was developed for the synthesis of a variety of chiral secondary alcohols. In the presence of a chiral oxazaborolidinium ion (COBI) catalyst, the reaction proceeded with good yields (up to 99%) with excellent enantioselectivities (up to 99% ee).