86521-05-3Relevant articles and documents
Regio- and stereoselective synthesis of bromoalkenes by homolytic hydrobromination of alkynes with hydrogen bromide
Kumaki, Wataru,Kinoshita, Hidenori,Miura, Katsukiyo
supporting information, (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.
Experimental and theoretical investigations into the manifestation of the γ-effect in 2- and 4-[2-silylethyl)]pyridines and pyridinium ions
Karnezis, Asimo,Brydon, Samuel C.,Molino, Andrew,Wilson, David J.D.,O'Hair, Richard A.J.,White, Jonathan M.
supporting information, (2021/09/08)
The γ-effect of the group 14 metals is a stabilizing interaction involving the back-lobe of the σC-M (M = Si, Ge, Sn, Pb) interacting with the developing carbocation γ to the tetrel. This percaudal interaction has been observed in solvolysis experiments with significant rate enhancements over unsubstituted systems, and subsequent isolation of three-membered ring products. In this study, the γ-effect is experimentally investigated in the solid phase with X-ray crystallography, the solution phase with Si-C coupling constants, and the gas phase via collision-induced dissociation (CID). Moving from 2- and 4-silylethyl substituted pyridines to the more electron demanding substituted pyridinium ion systems results in systematic shifts in key structural parameters including the 29Si-13C NMR coupling constants consistent with the cyclopropane-like resonance form attributable to the γ-effect. However, these shifts are much less in magnitude than those previously reported for the well documented β-effect. The gas phase CID results also reflect this with the fragmentation pathways for the silylethyl substituted systems not being dominated by the percaudal interaction, compared to previous studies where all major fragments were attributable to the β-effect. Density functional theory (DFT) calculated hyperhomodesmotic equations in combination with natural bond orbital (NBO) theory also supported the experimental trends with the γ-effect providing stabilization in the pyridinium ion systems studied, but to a much smaller extent to the β-effect.
Ru(II) coordination compounds of N[sbnd]N bidentate chelators with 1,2,3 triazole and isoquinoline subunits: Synthesis, spectroscopy and antimicrobial properties
Kreofsky, Nicholas W.,Dillenburg, Maxwell D.,Villa, Eric M.,Fletcher, James T.
supporting information, (2019/12/26)
Bidentate chelators 1-(1-benzyl-1,2,3-triazol-4-yl)isoquinoline and 3-(1-benzyl-1,2,3-triazol-4-yl)isoquinoline were prepared from benzyl bromide and trimethylsilylethynylisoquinoline precursors using a tandem deprotection/substitution/CuAAC synthetic approach. Each chelator is capable of forming a stable 3:1 Ru(II) coordination compound, which forms as a geometric isomer mixture. These Ru(II) complexes possess unique MLCT absorbance signatures at 450/472 nm (1-isomer) and 367 nm (3-isomer) relative to their constituent chelating units. Minimum inhibitory concentration values as low as 0.4 μM are observed for Ru(II) complexes against representative Gram-positive bacteria Bacillus subtilis and Staphylococcus epidermidis. Comparing the MIC values of these isoquinoline compounds with analogous 2-(1-benzyl-1,2,3-triazol-4-yl)pyridine compounds shows a 2.5- to 40-fold improvement in potency. This study establishes that increased hydrophobicity introduced at the central chelating units of Ru(II) coordination compounds can be a useful means by which to optimize antimicrobial activity that is complimentary to the variation of peripheral substituent identity at the chelator's N1 triazole position.
The synthesis of cyclometalated platinum(ii) complexes with benzoaryl-pyridines as C^N ligands for investigating their photophysical, electrochemical and electroluminescent properties
Wang, Dezhi,Chen, Xi,Yang, Hua,Zhong, Daokun,Liu, Boao,Yang, Xiaolong,Yue, Ling,Zhou, Guijiang,Ma, Miaofeng,Wu, Zhaoxin
supporting information, p. 15633 - 15645 (2020/11/24)
A series of (C^N)Pt(acac)-type complexes has been successfully synthesized with a benzo[b]furan, benzo[b]thiophene, benzo[b]selenophene, or benzo[b]tellurophene group in the benzoaryl-pyridine ligand. Using X-ray crystallography, the chemical structures o
Palladium (II) complexes chelated by 1-substituted-4-pyridyl-1H-1,2,3-triazole ligands as catalyst precursors for selective ethylene dimerization
Joseph, Mohammed Cassiem,Swarts, Andrew John,Mapolie, Selwyn Frank
, (2020/03/03)
A series of neutral as well as cationic palladium methyl complexes bearing 1-substituted-4-pyridyl-1H-1,2,3-triazole ligands were prepared and fully characterized by a range of analytical techniques. Conventional and 2D NMR spectroscopy as well as single-crystal X-ray diffraction analysis unambiguously determined the molecular structure of the complexes. The neutral complexes activated by methylaluminoxane were found to be effective catalysts in the ethylene dimerization reaction. The catalyst performance of the in-situ-generated active species was compared with the discrete cationic complexes of the same ligand scaffold. Activities and selectivities for the two systems were remarkably similar, pointing to similarities in the nature of the active species. Both catalytic systems showed a strong correlation of activity and selectivity with the nature of the ligand scaffold. Highest activities were attained when electron-withdrawing groups were incorporated into the triazole ring, while increasing steric bulk in the ortho-position on the pyridyl ring of the ligand led to the almost exclusive dimerization of ethylene with selectivities up to 94% observed toward 1-butene.
RET INHIBITORS, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
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Paragraph 00230; 00316; 00378, (2020/07/05)
Provided herein are a RET inhibitor, a pharmaceutical composition thereof and uses thereof. In particular, provided is a compound having Formula (I) or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof. Provided is a pharmaceutical composition comprising the compound, and uses of the compound and pharmaceutical composition thereof for the preparation of a medicament, in particular for treatment and prevention of RET-related diseases and conditions, including cancer, irritable bowel syndrome, and/or pain associated with irritable bowel syndrome.
BTK Inhibitors and uses thereof
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Paragraph 1600-1605, (2020/05/02)
The invention discloses a bruton's tyrosine kinase (BTK) inhibitor and use thereof. Specifically, the invention provides heteroaromatic compounds or stereoisomers, geometrical isomers, tautomers, racemates, nitrogen oxides, hydrates, solvates, metabolites and pharmaceutically acceptable salts or prodrugs thereof, and pharmaceutical compositions containing the heteroaromatic compounds; the invention also discloses use of the heteroaromatic compounds or the pharmaceutical compositions containing the heteroaromatic compounds in preparation of medicines; the medicines can be used for treating autoimmune diseases, inflammatory diseases or proliferative diseases.
Design and characterization of a heterocyclic electrophilic fragment library for the discovery of cysteine-targeted covalent inhibitors
Keeley,ábrányi-Balogh,Keseru
supporting information, p. 263 - 267 (2019/03/05)
A fragment library of electrophilic small heterocycles was characterized through cysteine-reactivity and aqueous stability tests that suggested their potential as covalent warheads. The analysis of theoretical and experimental descriptors revealed correlations between the electronic properties of the heterocyclic cores and their reactivity against GSH that are helpful in identifying suitable fragments for cysteines with specific nucleophilicity. The most important advantage of these fragments is that they show only minimal structural differences from non-electrophilic counterparts. Therefore, they could be used effectively in the design of targeted covalent inhibitors with minimal influence on key non-covalent interactions.
Trimethylsilyl-Protected Alkynes as Selective Cross-Coupling Partners in Titanium-Catalyzed [2+2+1] Pyrrole Synthesis
Chiu, Hsin-Chun,Tonks, Ian A.
supporting information, p. 6090 - 6094 (2018/05/30)
Trimethylsilyl (TMS)-protected alkynes served as selective alkyne cross-coupling partners in titanium-catalyzed [2+2+1] pyrrole synthesis. Reactions of TMS-protected alkynes with internal alkynes and azobenzene under the catalysis of titanium imido comple
Microwave-assisted copper- and palladium-catalyzed sonogashira-type coupling of aryl bromides and iodides with trimethylsilylacetylene
Lei, Yonghua,Hu, Tianhan,Wu, Xingsen,Wu, Yue,Xiang, Hua,Sun, Haopeng,You, Qidong,Zhang, Xiaojin
, p. 1100 - 1103 (2016/03/09)
An efficient and rapid method was developed for the synthesis of 1-aryl-2-(trimethylsilyl)acetylene. Copper and palladium-catalyzed sonogashira-type coupling of trimethylsilylacetylene and aryl bromides or iodides in the presence of triethylamine as base
