5834-16-2Relevant academic research and scientific papers
Regioselective electrophilic formylation - 3-substituted thiophenes as a case study
Meth-Cohn, Otto,Ashton, Mark
, p. 2749 - 2752 (2000)
A variety of methods for regioselective formylation have been examined and exemplified with 3-methylthiophene. Optimal yields and regioselectivity for 2-formylation were obtained with N-formylpyrrolidine (11:1) although up to a 46:1 ratio could be obtained with MeOCHCl2:TiCl4, albeit in lower yield. Optimal 5-formylation (1:1.5) was obtained when using N- formylindoline:(COCl)2. (C) 2000 Elsevier Science Ltd.
Synthesis and optical/electrochemical properties of meso-5,10,15,20-tetrathienyl substituted porphyrins and their metal complexes
Zhou, Yong,Liu, Fude,Wu, Haiyan,Qu, Boyang,Duan, Lijie
, p. 616 - 620 (2015)
Two kinds of meso-5,10,15,20-tetrathienyl substituted porphyrin compounds, meso-5,10,15,20-tetra(2-thienyl)porphyrin (H2TTP), meso-5,10,15,20-tetra(3-methyl-2-thienyl)porphyrin [H2T(3-M)TP] and their metal complexes were synthesized and characterized by IR, 1H NMR. UV-visible absorption spectra, fluorescence spectra, photoluminescence spectra and the cyclic voltammograms of the synthesized porphyrins and metalloporphyrins. Optical properties reveal that zinc porphyrin possesses intensive fluorescence emission, whereas cobalt(II) and copper(II) porphyrins exhibit no fluorescence emission. When the complexation of H2TTP and H2T(3-M)TP with metal ions occur, the electrochemical band-gaps (Eg) increase meanwhile the ELUMO shows smaller change than that of the EHOMO. The values of ionization potential, electronic affinity, HOMO energy level (EHOMO) and LUMO energy level (ELUMO) of the synthesized porphyrins and metalloporphyrins were also given in the paper.
Chemoselective Reduction of Sterically Demanding N,N-Diisopropylamides to Aldehydes
Xiao, Peihong,Tang, Zhixing,Wang, Kai,Chen, Hua,Guo, Qianyou,Chu, Yang,Gao, Lu,Song, Zhenlei
, p. 1687 - 1700 (2018/02/23)
A sequential one-pot process for chemoselectively reducing sterically demanding N,N-diisopropylamides to aldehydes has been developed. In this reaction, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The combination of EtOTf/2,6-DTBMP and LiAlH(O-t-Bu)3 was found to be optimal for reducing alkyl, alkenyl, alkynyl, and 2-monosubstituted aryl N,N-diisopropylamides. In contrast, EtOTf and LiAlH(OEt)3 in the absence of base were found to be optimal for reducing extremely sterically demanding 2,6-disubstituted N,N-diisopropylbenzamides. The reaction tolerates various reducible functional groups, including aldehyde and ketone. 1H NMR studies confirmed the formation of imidates stable in water. The synthetic usefulness of this methodology was demonstrated with N,N-diisopropylamide-directed ortho-metalation and C-H bond activation.
Palladium-catalyzed C-H formylation of electron-rich heteroarenes through radical dichloromethylation
Bao, Yan,Wang, Jian-Yong,Zhang, Ya-Xuan,Li, Yan,Wang, Xi-Sheng
supporting information, p. 3147 - 3150 (2018/07/13)
A novel palladium-catalyzed C-H formylation of electron-rich N-, O-, and S-containing heteroarenes has been developed. The key to success is that the commercially available BrCHCl2 was used as a stoichiometric carbonyl source. Mechanistic investigations indicated that different from the known Reimer-Tiemann reaction, this net C-H formylation proceeded through an electrophilc radical-type path.
Systematic structure-activity relationship (SAR) exploration of diarylmethane backbone and discovery of a highly potent novel uric acid transporter 1 (URAT1) inhibitor
Cai, Wenqing,Wu, Jingwei,Liu, Wei,Xie, Yafei,Liu, Yuqiang,Zhang, Shuo,Xu, Weiren,Tang, Lida,Wang, Jianwu,Zhao, Guilong
, (2018/02/07)
In order to systematically explore and better understand the structure-activity relationship (SAR) of a diarylmethane backbone in the design of potent uric acid transporter 1 (URAT1) inhibitors, 33 compounds (1a-1x and 1ha-1hi) were designed and synthesized, and their in vitro URAT1 inhibitory activities (IC50) were determined. The three-round systematic SAR exploration led to the discovery of a highly potent novel URAT1 inhibitor, 1h, which was 200-and 8-fold more potent than parent lesinurad and benzbromarone, respectively (IC50 = 0.035 μM against human URAT1 for 1h vs. 7.18 μM and 0.28 μM for lesinurad and benzbromarone, respectively). Compound 1h is the most potent URAT1 inhibitor discovered in our laboratories so far and also comparable to the most potent ones currently under development in clinical trials. The present study demonstrates that the diarylmethane backbone represents a very promising molecular scaffold for the design of potent URAT1 inhibitors.
Betti reaction enables efficient synthesis of 8-hydroxyquinoline inhibitors of 2-oxoglutarate oxygenases
Thinnes,Tumber,Yapp,Scozzafava,Yeh,Chan,Tran,Hsu,Tarhonskaya,Walport,Wilkins,Martinez,Müller,Pugh,Ratcliffe,Brennan,Kawamura,Schofield
supporting information, p. 15458 - 15461 (2015/10/20)
There is interest in developing potent, selective, and cell-permeable inhibitors of human ferrous iron and 2-oxoglutarate (2OG) oxygenases for use in functional and target validation studies. The 3-component Betti reaction enables efficient one-step C-7 functionalisation of modified 8-hydroxyquinolines (8HQs) to produce cell-active inhibitors of KDM4 histone demethylases and other 2OG oxygenases; the work exemplifies how a template-based metallo-enzyme inhibitor approach can be used to give biologically active compounds.
Synthesis of N-(Methoxycarbonylthienylmethyl)thioureas and evaluation of their interaction with inducible and neuronal nitric oxide synthase
Suaifan, Ghadeer A.R.Y.,Goodyer, Claire L.M.,Threadgill, Michael D.
experimental part, p. 3121 - 3134 (2010/09/04)
Two isomeric N-(memoxycarbonylmienylmemyl)mioureas were synthesised by a sequence of radical bromination of methylthiophenecarboxylic esters, substitution with trifluoroacetamide anion, deprotection, formation of the corresponding isothiocyanates and addition of ammonia. The interaction of these new thiophene-based thioureas with inducible and neuronal nitric oxide synthase was evaluauted. These novel thienylmethyl- thioureas stimulated the activity of inducible Nitric Oxide Synthase (iNOS).
Chiral helicenoid diarylethene with large change in specific optical rotation by photochromism
Okuyama, Tomoyuki,Tani, Yutaka,Miyake, Kentaro,Yokoyama, Yasushi
, p. 1634 - 1638 (2007/10/03)
A diarylethene possessing one [4]thiaheterohelicene and one benzothiophene, the latter with a chiral methoxymethoxyethyl group on its C-3 position, was proved to work as a switch of specific optical rotation at a wavelength at which both colored and colorless forms have no absorption in solution. The difference of the specific optical rotation was 1300° between the open form and the photostationary state. The specific optical rotation of one of the isolated optically active major colored forms was -4680°. The conversion to the colored form was 64%, and the diastereomeric excess of photocyclization was 47%.
Highly selective 5-substitution of 3-methylthiophene via directed lithiation
Smith, Keith,Barratt, Mark Lewis
, p. 1031 - 1034 (2008/02/04)
(Chemical Equation Presented) Lithiation of 3-methylthiophene with lithium 2,2,6,6-tetramethylpiperidide (LiTMP) is highly selective at the 5-position, and reaction with a range of electrophiles gives high yields of the corresponding 2,4-disubstituted thiophenes, even when unhindered electrophiles are used.
