3343-45-1

Usage

Synthesis Reference(s)

Canadian Journal of Chemistry, 30, p. 454, 1952 DOI: 10.1139/v52-054Tetrahedron Letters, 22, p. 1283, 1981 DOI: 10.1016/S0040-4039(01)90297-7

InChI:InChI=1/C8H7BrO2/c9-7-3-1-6(2-4-7)8(11)5-10/h1-4,10H,5H2

Upstream product

• 99-90-1 para-bromoacetophenone 
• 74087-85-7 3,3-dimethyldioxirane 
• 5391-88-8 1-(4-bromophenyl)ethanol 
• 32017-76-8 (+/-)-2-(4-bromophenyl)oxirane 
• 517-25-9 trinitromethane 
• 67-56-1 methanol 
• 55991-66-7 1-(4-bromophenyl)-1-(trimethylsilyloxy)ethylene 
• 766-96-1 4-bromo-1-ethynylbenzene 
• 1122-91-4 4-bromo-benzaldehyde 
• 298-12-4 Glyoxilic acid 
• 201403-02-3 (+/-)-2-amino-2-(4-bromophenyl)ethanol 
• 92093-23-7 1-(4-bromophenyl)ethane-1,2-diol 
• 2039-82-9 1-bromo-4-ethenyl-benzene 
• 57508-48-2 carbethoxyacetamidine hydrochloride 

Downstream Products

• 88690-88-4 2-(4-Bromphenyl)-2-ethoxyoxiran 
• 92093-23-7 (R)-(-)-1-(4-bromophenyl)-1,2-ethanediol 
• 850089-99-5 6-(4-bromophenyl)-3-(2-pyridyl)-1,2,4-triazine 
• 1394973-48-8 (4-bromophenyl)(5-chlorobenzo[d]thiazol-2-yl)methanone 
• 5195-29-9 4-bromophenylglyoxal 
• 140935-32-6 benzo[d]thiazol-2-yl(4-bromophenyl)methanone 
• 1383456-13-0 (E)-1-[2-hydroxy-4-(2-phenylethynyl)phenyl]-3-[4-(2-phenylethynyl)phenyl]prop-2-en-1-one 
• 1383935-31-6 1-(4-bromophenyl)-2,2-bis(1-methyl-1H-indol-3-yl)ethanone 
• 92093-23-7 1-(4-bromophenyl)ethane-1,2-diol 
• 1267440-90-3 1-(4-bromophenyl)-2-( piperidin-1-yl)ethane-1,2-dione 
• 1127405-08-6 1-(4-bromophenyl)-2-(morpholin-4-yl)ethane-1,2-dione 

Relevant academic research and scientific papers

Reactions of cephalosporin sulphones 1. Rearrangement of the β-lactam ring to a triazole derivative

The 7β-amino-cephalosporin sulphones, generated in situ from the appropriate 7β-tBoc-amino derivative and diazotized in a one-pot reaction in aq. HClO4 - MeOH - NaNO2, rearrange exclusively to the triazoles 5 in a multistep reaction.

Chiral Bidentate Phosphoramidite-Pd Catalyzed Asymmetric Decarboxylative Dipolar Cycloaddition for Multistereogenic Tetrahydrofurans with Cyclic N-Sulfonyl Ketimine Moieties

An asymmetric [3 + 2] cycloaddition of vinyl ethylenecarbonates (VECs) and (E)-3-arylvinyl substituted benzo[d] isothiazole 1,1-dioxides has been developed using the Pd complex of a bidentate phosphoramidite (Me-BIPAM) as the catalyst, providing a wide variety of chiral multistereogenic vinyltetrahydrofurans in good yields with excellent diastereo- and enantioselectivities (up to >20:1 dr, 99% ee).

Palladium-Catalyzed (3+3) Annulation of Allenylethylene Carbonates with Nitrile Oxides

In this paper, we designed and synthesized a new type of cyclic carbonates, allenylethylene carbonates (AECs). With AECs as reactive precursors, we developed palladium-catalyzed (3+3) annulation of AECs with nitrile oxides. Various AECs worked well in this reaction under mild reaction conditions. A variety of 5,6-dihydro-1,4,2-dioxazine derivatives with allenyl quaternary stereocenters can be accessed in a facile manner in high yields (≤98%).

Preparation and Application of α-Imino Ketones through One-Pot Tandem Reactions Based on Heyns Rearrangement

α-Imino ketone is a useful building block for the preparation of α-amino ketones and α-amino alcohols. However, its preparation has been seldomly seen. Herein, a metal-free and operationally simple strategy has been developed to generate α-imino ketones with high regioselectivity. Meanwhile, the method allowed for the preparation of various N,O-ketals with high regioselectivities and diastereoselectivities through cascade reactions in one pot.

Aerobic Direct Dioxygenation of Terminal/Internal Alkynes to α-Hydroxyketones by an Fe Porphyrin Catalyst

We herein report a new synthetic method for the preparation of α-hydroxyketones by the dioxygenation of alkynes. The reaction proceeds at room temperature under the action of Fe porphyrin and pinacolborane under air as a green oxidant to produce α-hydroxyketones. The mild reaction conditions allow chemoselective oxidation with functional group tolerance. Terminal alkynes in addition to internal alkynes are applicable, affording unsymmetrical α-hydroxyketones that are difficult to obtain by any reported dioxygenation of unsaturated C?C bonds.

One-Pot Enzymatic-Chemical Cascade Route for Synthesizing Aromatic α-Hydroxy Ketones

2-Hydroxyacetophenone (2-HAP) is an important building block for the production of a series of natural products and pharmaceuticals; however, there is no safe, efficient, and economical method for 2-HAP synthesis. Here, a one-pot enzymatic-chemical cascade route was designed for synthesizing 2-HAP based on retrosynthetic analysis. First, a spontaneous proton-transfer reaction was designed using a computational simulation that enabled 2-HAP synthesis from the isomer 2-hydroxy-2-phenylacetaldehyde. A route for 2-hydroxy-2-phenylacetaldehyde synthesis was then constructed by introducing the unnatural substrate glyoxylic acid into a C-C ligation reaction catalyzed by Candida tropicalis pyruvate decarboxylase. Assembly and optimization of this enzymatic-chemical cascade route resulted in a final yield of 92.7%. Furthermore, stereospecific carbonyl reductases were introduced to construct a synthetic application platform that enabled further transformation of 2-HAP into (S)- and (R)-1-phenyl-1,2-ethanediol. This method of cascading spontaneous chemical and enzymatic reactions to synthesize chemicals offers insight into avenues for synthesizing other valuable chemicals.

Enantioselective Cascade Biocatalysis for Deracemization of Racemic β-Amino Alcohols to Enantiopure (S)-β-Amino Alcohols by Employing Cyclohexylamine Oxidase and ω-Transaminase

Optically active β-amino alcohols are very useful chiral intermediates frequently used in the preparation of pharmaceutically active substances. Here, a novel cyclohexylamine oxidase (ArCHAO) was identified from the genome sequence of Arthrobacter sp. TYUT010-15 with the R-stereoselective deamination activity of β-amino alcohol. ArCHAO was cloned and successfully expressed in E. coli BL21, purified and characterized. Substrate-specific analysis revealed that ArCHAO has high activity (4.15 to 6.34 U mg?1 protein) and excellent enantioselectivity toward the tested β-amino alcohols. By using purified ArCHAO, a wide range of racemic β-amino alcohols were resolved, (S)-β-amino alcohols were obtained in >99 % ee. Deracemization of racemic β-amino alcohols was conducted by ArCHAO-catalyzed enantioselective deamination and transaminase-catalyzed enantioselective amination to afford (S)-β-amino alcohols in excellent conversion (78–94 %) and enantiomeric excess (>99 %). Preparative-scale deracemization was carried out with 50 mM (6.859 g L?1) racemic 2-amino-2-phenylethanol, (S)-2-amino-2-phenylethanol was obtained in 75 % isolated yield and >99 % ee.

Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors

The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.

Palladium-Catalyzed [5 + 2] Annulation of Vinylethylene Carbonates with Barbiturate-Derived Alkenes

A palladium/XantPhos-catalyzed [5 + 2] annulation of VECs with electron-deficient alkenes having an isolated carbon-carbon double bond has been developed to afford spirobarbiturate-tetrahydrooxepines. This study provides an expedient assembly of biologically interesting spirobarbiturate-tetrahydrooxepines. The easy scalability and versatile transformability of the reaction products were also exhibited.

Palladium-Catalyzed Diastereoselective Formal [5 + 3] Cycloaddition for the Construction of Spirooxindoles Fused with an Eight-Membered Ring

A Pd-catalyzed formal [5 + 3] intermolecular cycloaddition reaction of isatin-derived α-(trifluoromethyl)imines with aryl substituted vinylethylene carbonates (VECs) has been reported, affording trifluoromethyl-group-containing spirooxindoles fused with an eight-membered ring as a single diastereoisomer in good yields in the presence of a Br?nsted acid in a one-pot manner under mild conditions. The asymmetric version of this reaction has been also realized using a chiral phosphine ligand along with the further transformation of the obtained product to give a spirooxindolo pyrrolidine derivative upon oxidation.