1074-15-3

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 49, p. 4226, 1984 DOI: 10.1021/jo00196a024

InChI:InChI=1/C8H8Br2/c9-6-5-7-3-1-2-4-8(7)10/h1-4H,5-6H2

Upstream product

• 694-87-1 benzocyclobutene 
• 1074-16-4 2-bromophenylethyl alcohol 
• 103-82-2 phenylacetic acid 
• 113163-19-2 2-(2'bromophenyl)-1-iodoethane 
• 2039-88-5 2-bromostyrene 
• 3433-80-5 1-Bromo-2-bromomethyl-benzene 
• 19472-74-3 2-(2-bromophenyl)acetonitrile 
• 18698-97-0 ortho-bromophenylacetic acid 
• 2183-83-7 methanesulfonic acid 2-(2-bromophenyl)ethyl ester 

Downstream Products

• 345294-39-5 1'-benzylspiro 
• 162395-63-3 7-(2'-bromophenyl)-5,5-bis(ethoxycarbonyl)-1,2-heptadiene 
• 92013-28-0 1,1-bis(ethoxycarbonyl)-3-(2'-bromophenyl)propane 
• 174710-24-8 2-<2-(o-bromophenyl)ethyl>-2-(trimethylsilyl)-1,3-dithiane 
• 183789-25-5 N-[2-(2-Bromo-phenyl)-ethyl]-N-propa-1,2-dienyl-benzenesulfonamide 
• 174710-33-9 3-(2-Bromo-phenyl)-1-(methyl-diphenyl-silanyl)-propan-1-one 
• 172484-96-7 (1S,2R)-4-Bromo-3-(2-bromo-ethyl)-cyclohex-3-ene-1,2-diol 
• 65185-58-2 2-(2-bromophenyl)ethanamine 
• 75780-68-6 N-benzylidene-β-(2-bromophenyl)ethylamin 
• 22990-19-8 1-phenyl-1,2,3,4-tetrahydroisoquinoline 
• 468-10-0 morphine 
• 54877-20-2 C₆H₄CH₂CH₂Sn(C₆H₅)2 
• 545411-28-7 1-bromomercurio-[2-(2-bromommercurio)ethyl]benzene 
• 1382354-31-5 2-{3-(2-bromophenethoxy)phenylamino}benzamide 

Relevant academic research and scientific papers

Synthesis of 2,3-dihydro-1-phenylbenzo[b]phosphole (1-phenylphosphindane) and its use as a mechanistic test in the asymmetric appel reaction: Decisive evidence against involvement of pseudorotation in the stereoselecting step

Racemic 2,3-dihydro-1-phenylbenzo[b]phosphole was obtained by reduction of 1-phenylbenzo[b]phosphole-1-oxide, itself derived by ring-closing metathesis of phenylstyrylvinylphosphine oxide. The title compound was then reoxidized under asymmetric Appel cond

Site- and regio-selective incorporation of carbon dioxide into the C(sp2)Si bond of benzosilacyclobutenes

A reaction of benzosilacyclobutenes with carbon dioxide is catalyzed by a nickel complex having an N-heterocyclic carbene ligand. Carbon dioxide inserts into the C(sp2)Si bond in a site- and regio-selective manner to form a carboncarbon bond, furnishing benzoic acid derivatives.

Enantio- and diastereotopos differentiation in the palladium(II)-catalyzed hydrosilylation of bicyclo[2.2.1]alkene scaffolds with silicon-stereogenic silanes

The palladium(II)-catalyzed hydrosilylation of meso-configured bicyclo[2.2.1]alkene scaffolds proved to be an invaluable model reaction for the development of reagent-controlled asymmetric transformations based on silicon-stereogenic silanes as stereoinducers. In the present investigation, the subtle structural requirements of the silane substitution pattern in enantiotopos-differentiating single hydrosilylations of a norbornene-type substrate are disclosed. Extension of this chemistry to a double hydrosilylation of norbornadiene entails a significant increase in stereochemical complexity. Although differentiation of enantiotopic positions by the chiral reagent is demanded in the first hydrosilylation, the same reagent must then differentiate diastereotopic positions in the second. Remarkably high stereocontrol was found in this double hydrosilylation with several silanes first used in the hydrosilylations of the norbornene-type system. Depending on the enantiomeric purity of the silane, C2- and Cs-symmetric adducts, respectively, were obtained. The identity of the key quaternary silanes was revealed by crystallographic analysis. By this method, the relative and absolute configurations were also assigned, which, in turn, imply that all enantiospecific substitutions at silicon proceed with stereoretention. On the basis of these solid-state structures, we also discuss the structural implications of silane substitution for the diastereoselectivity-determining step of this palladium(II)-catalyzed hydrosilylation reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes

An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.

Synthesis and Structure-Affinity Relationships of Spirocyclic Benzopyrans with Exocyclic Amino Moiety

σ1 and/or σ2 receptors play a crucial role in pathological conditions such as pain, neurodegenerative disorders, and cancer. A set of spirocyclic cyclohexanes with diverse O-heterocycles and amino moieties (general structure III) was prepared and pharmacologically evaluated. In structure-activity relationships studies, the σ1 receptor affinity and σ1:σ2 selectivity were correlated with the stereochemistry, the kind and substitution pattern of the O-heterocycle, and the substituents at the exocyclic amino moiety. cis-configured 2-benzopyran cis-11b bearing a methoxy group and a tertiary cyclohexylmethylamino moiety showed the highest σ1 affinity (Ki = 1.9 nM) of this series of compounds. In a Ca2+ influx assay, cis-11b behaved as a σ1 antagonist. cis-11b reveals high selectivity over σ2 and opioid receptors. The interactions of the novel σ1 ligands were analyzed on the molecular level using the recently reported X-ray crystal structure of the σ1 receptor protein. The protonated amino moiety forms a persistent salt bridge with E172. The spiro[benzopyran-1,1′-cyclohexane] scaffold and the cyclohexylmethyl moiety occupy two hydrophobic pockets. Exchange of the N-cyclohexylmethyl moiety by a benzyl group led unexpectedly to potent and selective μ-opioid receptor ligands.

COMPOUNDS, COMPOSITIONS AND METHODS FOR SYNTHESIS

The present disclosure, among other things, provides technologies for synthesis, including reagents and methods for stereoselective synthesis. In some embodiments, the present disclosure provides compounds useful as chiral auxiliaries. In some embodiments, the present disclosure provides reagents and methods for oligonucleotide synthesis. In some embodiments, the present disclosure provides reagents and methods for chirally controlled preparation of oligonucleotides. In some embodiments, technologies of the present disclosure are particularly useful for constructing challenging internucleotidic linkages, providing high yields and stereoselectivity.

Highly diastereoselective synthesis of tetralin-fused spirooxindoles via lewis acid-catalyzed C(sp3)H bond functionalization

A highly diastereoselective synthesis of tetralin-fused spirooxindole derivatives was described. Treatment of benzylidene oxindoles with a catalytic amount of Sc(OTf)3 in refluxing hexane afforded the target compounds in good chemical yields with excellent diastereoselectivities (up to >20:1). Detailed investigation of the reaction mechanism revealed that both interconversion of the two diastereomers and their solubility difference in reaction medium were the key to achieving excellent diastereoselectivities.

9-Silafluorenyl Dichlorides as Chemically Ligating Coupling Agents and Their Application in Peptide Synthesis

A fundamentally simple, mild, and practical procedure for peptide bond formation is reported that employs a stoichiometric amount of easy-to-access 9-silafluorenyl dichlorides as the coupling agent. Without initial preactivation or elaboration of the carboxylic acid or amine termini of the amino acids, the developed reagent is proposed to act through an unprecedented chemical ligation mechanism, bringing the two coupling partners together before being subsequently eliminated. The desired amides or peptide bonds are thus furnished in good yields and with low to no epimerization.

Scalable anti-Markovnikov hydrobromination of aliphatic and aromatic olefins

To improve access to a key synthetic intermediate we targeted a direct hydrobromination-Negishi route. Unsurprisingly, the anti-Markovnikov addition of HBr to estragole in the presence of AIBN proved successful. However, even in the absence of an added initiator, anti-Markovnikov addition was observed. Re-examination of early reports revealed that selective Markovnikov addition, often simply termed "normal" addition, is not always observed with HBr unless air is excluded, leading to the rediscovery of a reproducible and scalable initiator-free protocol.

Construction of chiral 2-substituted octahydroindoles from cyclic ketones and nitroolefins bearing only one α-substituent

A dual catalytic system has been developed following the screening of a series of chiral primary amine catalysts and chiral phosphoric acid catalysts for the Michael addition of cyclic ketones to nitroolefins bearing only one α-substituent. The resulting γ-nitro ketones, which contain a substituent on the carbon connected to the nitro group, were formed in excellent yields (>80%) with high levels of stereoselectivity (up to 94:6 dr and 98% ee) when the reaction was performed in benzene at 0 °C with 10 mol% of the optimal amine/phosphoric acid combination (1:1) as a catalyst. Subsequent reduction of the nitro group followed by intramolecular reductive amination could afford optically active cis-octahydroindole analogues bearing a non-functional substituent at their 2-position.