142052-64-0

Upstream product

• 14371-10-9 (E)-3-phenylpropenal 
• 70110-65-5 2-phenoxy-1-phenylpropane-1, 3-diol 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 104-54-1 3-Phenylpropenol 

Downstream Products

• 105908-80-3 acetimidic acid-((2RS,3SR)-2,3-dibromo-3-phenyl-propyl ester) 
• 52124-00-2 (3-phenyl-2H-azirin-2-yl)methanol 
• 192370-02-8 (S)-(+)-phenyl-2H-azirine-2-methanol 
• 98948-21-1 (2RS,3SR)-2,3-dibromo-3-(4-nitro-phenyl)-propan-1-ol 
• 99853-44-8 (1RS,2SR)-3-acetoxy-1,2-dibromo-1-(4-nitro-phenyl)-propane 
• 101272-36-0 (1RS,2SR)-3-benzoyloxy-1,2-dibromo-1-(4-nitro-phenyl)-propane 
• 66820-54-0 β-bromocinnamyl alcohol 
• 4801-14-3 3,3-diphenylprop-2-en-1-ol 
• 141811-76-9 (2RS,3SR)-3-bromo-3-phenyl-1,2-epoxypropane 
• 101167-32-2 benzoic acid-((2RS,3RS)-2-amino-3-bromo-3-phenyl-propyl ester) 
• 73405-87-5 N-((1RS,2RS)-2-bromo-1-bromomethyl-2-phenyl-ethyl)-benzamide 
• 102548-60-7 benzoic acid-((1RS,2SR)-2-amino-3-bromo-1-phenyl-propyl ester) 

Relevant academic research and scientific papers

Use of WO42- on layered double hydroxides for mild oxidative bromination and bromide-assisted epoxidation with H2O2

Tungstate, exchanged on a (Ni, Al) layered double hydroxide, is applied as a heterogeneous catalyst in the oxidation of bromide with H2O2 and the ensuing electrophilic bromination of olefins. The high halogenation activity of the catalyst in essentially neutral conditions mimicks the activity of V-bromoperoxidase enzymes. In water, aromatic and aliphatic olefins are selectively converted to bromohydrins; in methanol, methoxybromides are produced. In appropriate solvent conditions, the bromohydroxylation of geminally di-, tri-, and tetrasubstituted olefins proceeds via dehydrobromination to the epoxide. Evidence for this mechanism is provided by kinetic and labeling experiments. This one-pot alternative for the two-step halohydrin epoxidation process is enabled by the mild pH conditions; bromide is effective in substoichiometric, catalytic amounts. All new catalytic procedures are characterized by a high oxidative stability of the catalyst, high productivity of the catalyst on weight basis, high W turnover frequencies in ambient conditions (up to 50 mol of product per W per h), and high chemo-, regio-, and stereoselectivities.

Stereoselective synthesis of (E)-3,3-diaryl and (E)-3-aryl-3-aryloxy allylamines and allylalcohols from trans-cinnamyl chloride and alcohol

In this work we describe the regio and stereoselective synthesis of (E)-3,3-diaryl and (E)-3-aryl-3-aryloxy allylamines and allylalcohols. The starting materials are the non-expensive commercially available cinnamyl alcohol and chloride. The bromination/dehydrobromination sequence furnished the (E)-3-bromo-3-phenylallyl amines and alcohol as single regioisomers and with high stereoselectivity (>98%). These vinyl bromides were used as substrates in cross-coupling reactions furnishing the arylated products with good to excellent yields and total E-configuration retention. With this protocol, we were able to produce regio and stereospecifically trisubstituted olefins and vinyl ethers by Suzuki cross-coupling and Ullmann vinylation.

BBr3-Assisted Preparation of Aromatic Alkyl Bromides from Lignin and Lignin Model Compounds

For the first time, BBr3-assisted nucleophilic substitution was applied to a variety of β-O-4 and α-O-4 model compounds for the highly effective cleavage of different C-O bonds, including C-Oα-OH, Cβ-O/Cα-O and CMe-O bonds (99% conversion for most cases). Without any pretreatment, the substitution proceeds at room temperature in the absence of any catalyst, or additive, selectively affording phenols and important organic synthesis reagents, aromatic alkyl bromides, in high to excellent yields (up to 98%). Preliminary studies also highlight the prospect of this method for the effective cleavage of different types of C-O bonds in real lignin. A total 14 wt % yield of aromatic alkyl bromide, 4-(1,2-dibromo-3-hydroxypropyl)benzene-1,2-diol (10), has been obtained from an extracted lignin through this method.

Dibromination of alkenes with LiBr and H2O2 under mild conditions

Electron-rich and electron-poor alkenes, and alkenes bearing protecting groups can be efficiently and stereoselectively converted to trans-dibromides using LiBr/H2O2 and AcOH as a proton source in 1,4-dioxane. For most substrates addition of 0.1 mol% of PhTeTePh enhances the reaction rate and the yield of the products. Experimental data suggest that the brominating agent prepared in situ is molecular bromine and that LiBr assists the activation of H2O2 allowing bromination to occur using AcOH as a mild proton source in uncatalyzed experiments. Scale-up is feasible: 10.0 mmol of 1-octene was quantitatively converted to 1,2-dibromooctene in one hour of reaction at room temperature.

Multicomponent Synthesis of Structurally Diverse Imidazoles Featuring Azirines, Amines and Aldehydes

A novel and efficient method for the synthesis of structurally diverse imidazoles through a multicomponent reaction involving an azirine, an amine, and an aldehyde is described. The method is simple and environmentally benign, producing multifunctionalized imidazoles in moderate-to-good yields and in a regioselective manner, which was demonstrated by NMR experiments and X-ray analysis. A mechanism is proposed in which the amine participates not only as a reactant, but also as a nucleophilic reaction promoter.

Catalytic Enantioselective Dihalogenation and the Selective Synthesis of (-)-Deschloromytilipin A and (-)-Danicalipin A

A titanium-based catalytic enantioselective dichlorination of simple allylic alcohols is described. This dichlorination reaction provides stereoselective access to all common dichloroalcohol building blocks used in syntheses of chlorosulfolipid natural products. An enantioselective synthesis of ent-(-)-deschloromytilipin A and a concise, eight-step synthesis of ent-(-)-danicalipin A are executed and employ the dichlorination reaction as the first step. Extension of this system to enantioselective dibromination and its use in the synthesis of pentabromide stereoarrays relevant to bromosulfolipids is reported. The described dichlorination and dibromination reactions are capable of exerting diastereocontrol in complex settings allowing X-ray crystal structure analysis of natural and unnatural diastereomers of polyhalogenated stereohexads.

Halocarbocyclization versus dihalogenation: Substituent directed iodine(iii) catalyzed halogenations

The nucleophilicity of the substituents in iodobenzene pre-catalysts have a huge impact on product selectivity in iodine(iii) triggered halogenations, steering the reactivity from solely carbocyclizations towards dihalogenations. Utilizing this catalyst-dependent reactivity a diastereo- and chemoselective dihalogenation method was established allowing the conversion of structurally and electronically diverse unsaturated compounds in excellent yields.

Catalytic enantioselective dibromination of allylic alcohols

A new dibromination reaction involving the combination of dibromomalonate as the bromonium source and a titanium bromide species as the bromide source has been developed. Enantioselective catalysis has been achieved through apparent ligand acceleration by a tartaric acid-derived diol.

Regio-and stereoselective hydroxybromination and dibromination of olefins using ammonium bromide and oxone

An efficient protocol for the synthesis of vicinal bromohydrins and dibromides from olefins is presented. Various olefins are regio-and stereoselectively hydroxybrominated and dibrominated with anti fashion, following Markonikov's rule, using eco-friendly, non-toxic, and stable reagents such as NH4Br and oxone in CH3CN/H2O (1:1) and CH3CN without employing catalyst in moderate to excellent yields. Bromohydrins are formed instantaneously.

Organocatalytic diastereoselective dibromination of alkenes

A highly diastereoselective pyrrolidine-promoted dibromination of alkenes by combination of NBS and succinimide is presented. The pyrrolidine-mediated dibromination of alkenes is higly anti-selective and gives the corresponding products in moderate to high yields and up to >25:1 dr.