588-73-8Relevant articles and documents
On the planarity of styrene and its derivatives: The molecular structures of styrene and (Z)-β-bromostyrene as determined by ab initio calculations and gas-phase electron diffraction
Cochran, John C.,Hagen, Kolbjorn,Paulen, Gunnar,Shen, Quang,Tom, Samson,Traetteberg, Marit,Wells, Christopher
, p. 313 - 326 (1997)
The molecular structures of styrene and (Z)-β-bromostyrene have been studied in the gas phase at nozzle temperatures of 303 and 338 K respectively. For both molecules the electron diffraction data were consistent with the results from ab initio calculatio
Regio- and stereoselective synthesis of bromoalkenes by homolytic hydrobromination of alkynes with hydrogen bromide
Kumaki, Wataru,Kinoshita, Hidenori,Miura, Katsukiyo
, (2022/03/07)
Homolytic hydrobromination of terminal and internal alkynes with a commercially available solution of hydrogen bromide in acetic acid has been investigated for regio- and stereoselective synthesis of bromoalkenes. Under an aerobic atmosphere at room temperature, the reaction of ethynylarenes with a small excess of HBr efficiently gave (2-bromoethenyl)arenes with good to high E-selectivity. (Alk-1-ynyl)arenes, or internal alkynes bearing both phenyl and alkyl groups at the sp-carbons also underwent the air-initiated hydrobromination to exhibit high Z-selectivity under kinetic conditions using a half equivalent of HBr.
Chemical validation of a druggable site on Hsp27/HSPB1 using in silico solvent mapping and biophysical methods
Makley, Leah N.,Johnson, Oleta T.,Ghanakota, Phani,Rauch, Jennifer N.,Osborn, Delaney,Wu, Taia S.,Cierpicki, Tomasz,Carlson, Heather A.,Gestwicki, Jason E.
, (2021/02/09)
Destabilizing mutations in small heat shock proteins (sHsps) are linked to multiple diseases; however, sHsps are conformationally dynamic, lack enzymatic function and have no endogenous chemical ligands. These factors render sHsps as classically “undruggable” targets and make it particularly challenging to identify molecules that might bind and stabilize them. To explore potential solutions, we designed a multi-pronged screening workflow involving a combination of computational and biophysical ligand-discovery platforms. Using the core domain of the sHsp family member Hsp27/HSPB1 (Hsp27c) as a target, we applied mixed solvent molecular dynamics (MixMD) to predict three possible binding sites, which we confirmed using NMR-based solvent mapping. Using this knowledge, we then used NMR spectroscopy to carry out a fragment-based drug discovery (FBDD) screen, ultimately identifying two fragments that bind to one of these sites. A medicinal chemistry effort improved the affinity of one fragment by ~50-fold (16 μM), while maintaining good ligand efficiency (~0.32 kcal/mol/non-hydrogen atom). Finally, we found that binding to this site partially restored the stability of disease-associated Hsp27 variants, in a redox-dependent manner. Together, these experiments suggest a new and unexpected binding site on Hsp27, which might be exploited to build chemical probes.
Stable and Highly Regioselective Anionic Polymerization of (Z)-1-Phenyl[3]dendralene
Miya, Masamitsu,Takagi, Tsukasa,Takenaka, Katsuhiko,Toda, Tomoyuki
, p. 4326 - 4332 (2021/05/29)
The anionic polymerization of (Z)-1-phenyl[3]dendralene (1Z-P3D) in THF with potassium naphthalenide (K-Naph) as an initiator was investigated. At -78 °C, a polymer of predictable molecular weight and narrow molecular-weight distribution (Mw/Mn = 1.26) was obtained quantitively in 24 h. The active chain-end carbanion derived from 1Z-P3D was significantly stabilized by conjugation with a phenyl substituent at the C1 position of the monomer; side reactions such as nucleophilic addition to the double bond in other polymer main chains were not observed over a wide temperature range (-78-0 °C). The microstructure of the obtained poly(1Z-P3D) contained a predominant amount of the 1,4 structure (>90%). Thus, the polymerizability of 1Z-P3D was different from that of previously reported 2-phenyl[3]dendralene (P3D), in terms of the nucleophilicity of the active chain end and regioselectivity in the propagation reaction.
Illuminatinganti-hydrozirconation: controlled geometric isomerization of an organometallic species
Gilmour, Ryan,Hostmann, Theresa,Nevesely, Tomá?
, p. 10643 - 10648 (2021/08/20)
A general strategy to enable the formalanti-hydrozirconation of arylacetylenes is reported that mergescis-hydrometallation using the Schwartz Reagent (Cp2ZrHCl) with a subsequent light-mediated geometric isomerization atλ= 400 nm. Mechanistic delineation of thecontra-thermodynamic isomerization step indicates that a minor reaction product functions as an efficientin situgenerated photocatalyst. Coupling of theE-vinyl zirconium species with an alkyne unit generates a conjugated diene: this has been leveraged as a selective energy transfer catalyst to enableE→Zisomerization of an organometallic species. Through anUmpolungmetal-halogen exchange process (Cl, Br, I), synthetically useful vinyl halides can be generated (up toZ?:?E= 90?:?10). This enabling platform provides a strategy to access nucleophilic and electrophilic alkene fragments in both geometric forms from simple arylacetylenes.
Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes
Iakovenko, Roman,Hlavá?, Jan
, p. 440 - 446 (2021/01/28)
Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is
Method for synthesizing beta-bromostyrene through metal-free catalysis
-
Paragraph 0023-0028; 0031-0033, (2020/02/06)
The invention discloses a method for synthesizing beta-bromostyrene through metal-free catalysis, and belongs to the technical field of organic chemistry. Substituted styrene 1 is used as a raw material and is reacted in the presence of a bromination reagent, sodium persulfate and dichloroethane, and the beta-bromostyrene compound 2 can be obtained in one step. The method is capable of solving thetechnical problem that in the traditional synthesis method, conversion into alkenyl boron, alkenyl silicon and other intermediates under the catalysis of noble metals and then further halogenation are needed; the defects of expensive reaction reagent, high catalytic cost, complex operation, incapability of large-scale preparation and the like in the traditional preparation method are avoided; byadopting the method, a series of beta-bromostyrene compounds can be obtained, and the method has a potential application prospect.
Facile Synthesis of β-Bromostyrenes by Direct Bromination of Styrenes with N -Bromosuccinimide and Sodium Persulfate
Chen, Xuenian,Gao, Yan,Jing, Yi,Ma, Yan-Na,Zhao, Qianyi
supporting information, (2020/09/09)
A new, direct, efficient, and transition-metal-free method is reported for the synthesis of β-bromostyrenes from styrenes by using N -bromosuccinimide as the brominating reagent and sodium persulfate (Na 2S 2O 8) as the oxidant. This convenient and concise reaction is practical, operationally simple, and can be adapted for large-scale syntheses.
Photocatalytic Isomerization of Styrenyl Halides: Stereodivergent Synthesis of Functionalized Alkenes
Zhang, Hao,Xu, Qing,Yu, Lei,Yu, Shouyun
supporting information, p. 1472 - 1477 (2019/11/03)
An efficient and general method for the isomerization of styrenyl halides under different photocatalytic conditions (fac-Ir(ppy)3 in methanol for E to Z isomerization and fluorescein in 1,4-dioxane for Z to E isomerization, respectively) is disclosed. A series of stereospecific transformations constitute preliminary validation of this strategy in the synthesis of functionalized alkenes, including two diaryl alkenes, a styrenyl boronic ester and an enyne. The photocatalytic isomerization and subsequent cross coupling reaction can be run in a one-pot manner. The stereodivergent synthesis of all four isomers of a conjugated diene, as well as the antitumor agent DMU-212 and its (Z)-isomer highlights the synthetic applicability of this method.
Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium-Catalyzed Carbonylation
Domino, Katrine,Veryser, Cedrick,Wahlqvist, Benjamin A.,Gaardbo, Cecilie,Neumann, Karoline T.,Daasbjerg, Kim,De Borggraeve, Wim M.,Skrydstrup, Troels
supporting information, p. 6858 - 6862 (2018/05/08)
A palladium-catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α-bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late-stage carbon-isotope labeling.
