- Intermolecular locking design of red thermally activated delayed fluorescence molecules for high-performance solution-processed organic light-emitting diodes
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Design of high-performance red thermally activated delayed fluorescence (TADF) materials remains a great challenge owing to their small energy bandgaps with severe nonradiative decay for low luminous efficiency. Introducing rigid and fused moieties is an
- Jin, Jibiao,Wang, Wuji,Xue, Peiran,Yang, Qingqing,Jiang, He,Tao, Ye,Zheng, Chao,Xie, Guohua,Huang, Wei,Chen, Runfeng
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- 1,3-Diradicals Embedded in Curved Paraphenylene Units: Singlet versus Triplet State and In-Plane Aromaticity
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Curved π-conjugated molecules and open-shell structures have attracted much attention from the perspective of fundamental chemistry, as well as materials science. In this study, the chemistry of 1,3-diradicals (DRs) embedded in curved cycloparaphenylene (
- Miyazawa, Yuki,Wang, Zhe,Matsumoto, Misaki,Hatano, Sayaka,Antol, Ivana,Kayahara, Eiichi,Yamago, Shigeru,Abe, Manabu
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supporting information
p. 7426 - 7439
(2021/05/29)
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- Chiral thermally-activated delayed fluorescence material, and preparation method and application thereof
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The invention discloses a chiral thermally-activated delayed fluorescence material, and a preparation method and application thereof. Through molecular design, an axial chiral induction center, an electron withdrawing group boric acid ester and a pluralit
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Paragraph 0017; 0054-0057; 0061-0064
(2021/06/13)
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- I2-Promoted [3+2] Cyclization of 1,3-Diketones with Potassium Thiocyanate: a Route to Thiazol-2(3H)-One Derivatives
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An I2-promoted strategy has been developed for the synthesis of thiazol-2(3H)-one derivatives from 1,3-diketones with potassium thiocyanate. This [3+2] cyclization reaction involves C?S and C?N bond formation and exhibits good functional group tolerance. A series of thiazol-2(3H)-one derivatives are obtained in moderate to good yields. (Figure presented.).
- An, Zhenyu,Liu, Yafeng,Yan, Rulong,Zhao, Pengbo
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supporting information
p. 3240 - 3244
(2021/06/16)
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- NOVEL HETEROAROMATIC COMPOUNDS EXHIBITING ANTIFUNGAL ACTIVITY AND THEIR METHOD OF USE
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Pharmaceutical compositions of the invention comprise herteroaromatic compounds having a disease-modifying action in the treatment of fungal infections and diseases associated with fungal infection.
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Paragraph 0768-0769
(2021/12/28)
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- 1,2-Diazacyclopentane-3,5-diyl Diradicals: Electronic Structure and Reactivity
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Localized singlet diradicals are key intermediates in bond homolysis. A thorough study of the reactive species is needed to clarify the mechanisms of the homolytic bond cleavage and formation processes. In general, the singlet diradicals are quite short-lived because of the fast radical-radical coupling reactions. The short-lived characteristic has retarded the thorough study on bond homolysis. In this study, a new series of long-lived singlet diradicals, viz., 1,2-diazacyclopentane-3,5-diyl, were identified, and their electronic structures and novel reactivities were thoroughly studied using laser-flash photolysis (LFP), product analysis, and computational studies. A direct observation of the thermal equilibration (fast process) between the singlet diradicals and the corresponding ring-closing compounds was undertaken on the submicrosecond time scale. The solvent and substituent effects on the equilibration constant and rate constants for the ring-closing reaction and ring-opening reaction clarify the novel nitrogen-atom effect on the localized singlet 1,3-diyl diradicals. Two types of alkoxy-migrated compounds, 9 and 10, were isolated with high yields as the final products. Crossover, spin-trapping, and LFP experiments for the formation of alkoxy-group migration products (i.e., 9 versus 10) revealed the unique temperature effect on the product ratio of the two types of alkoxy-migration products. The temperature-insensitive intersystem crossing process (slow process, millisecond time scale) was found to be a key step in the formation of 9, which is an entropy-controlled pathway. An intramolecular migration process was identified for the formation of 10 that was accelerated by a polar solvent in an enthalpy-controlled process. This unique heteroatom effect has opened up a new series of localized singlet diradicals that are crucial intermediates in bond homolysis.
- Yoshidomi, Shohei,Abe, Manabu
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supporting information
p. 3920 - 3933
(2019/03/07)
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- Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones
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A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.
- He, Zhen,Qi, Xiaotian,She, Zhijie,Zhao, Yinsong,Li, Shiqing,Tang, Junbin,Gao, Ge,Lan, Yu,You, Jingsong
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supporting information
p. 1403 - 1411
(2017/02/10)
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- Regioselective Rhodium-Catalyzed Addition of 1,3-Dicarbonyl Compounds to Terminal Alkynes
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A new method for the rhodium-catalyzed regioselective C-C bond formation using terminal alkynes and 1,3-dicarbonyl compounds to achieve valuable branched α-allylated 1,3-dicarbonyl products is reported. With a Rh(I)/DPEphos/p-CF3-benzoic acid as the catalyst system, the desired products can be obtained in good to excellent yields and with perfect regioselectivity. A broad range of functional groups were tolerated, and first experimental insights of a plausible reaction mechanism were obtained.
- Beck, Thorsten M.,Breit, Bernhard
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supporting information
p. 124 - 127
(2016/01/15)
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- 2,2-Difluoro-1,3-diketones as gem-Difluoroenolate Precusors for Asymmetric Aldol Addition with N-Benzylisatins
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2,2-Difluoro-1,3-diketones are introduced as gem-difluoroenolate precursors for the first example of an organocatalytic asymmetric aldol addition with N-benzylisatins to form 3-difluoroalkyl-3-hydroxyoxindoles. (Figure presented.).
- Qian, Jinlong,Yi, Wenbin,Huang, Xin,Jasinski, Jerry P.,Zhang, Wei
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p. 2811 - 2816
(2016/09/13)
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- Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes
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An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.
- Yang, Ning-Yuan,Li, Zhong-Liang,Ye, Liu,Tan, Bin,Liu, Xin-Yuan
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supporting information
p. 9052 - 9055
(2016/07/21)
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- Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
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A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
- He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
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p. 855 - 859
(2015/02/05)
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- Structure-based design, synthesis and evaluation in vitro of arylnaphthyridinones, arylpyridopyrimidinones and their tetrahydro derivatives as inhibitors of the tankyrases
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Abstract The tankyrases are members of the PARP superfamily; they poly(ADP-ribosyl)ate their target proteins using NAD+ as a source of electrophilic ADP-ribosyl units. The three principal protein substrates of the tankyrases (TRF1, NuMA and axin) are involved in replication of cancer cells; thus inhibitors of the tankyrases may have anticancer activity. Using structure-based drug design and by analogy with known 3-arylisoquinolin-1-one and 2-arylquinazolin-4-one inhibitors, series of arylnaphthyridinones, arylpyridinopyrimidinones and their tetrahydro-derivatives were synthesised and evaluated in vitro. 7-Aryl-1,6-naphthyridin-5-ones, 3-aryl-2,6-naphthyridin-1-ones and 3-aryl-2,7-naphthyridin-1-ones were prepared by acid-catalysed cyclisation of the corresponding arylethynylpyridinenitriles or reaction of bromopyridinecarboxylic acids with β-diketones, followed by treatment with NH3. The 7-aryl-1,6-naphthyridin-5-ones were methylated at 1-N and reduced to 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones. Cu-catalysed reaction of benzamidines with bromopyridinecarboxylic acids furnished 2-arylpyrido[2,3-d]pyrimidin-4-ones. Condensation of benzamidines with methyl 1-benzyl-4-oxopiperidine-3-carboxylate and deprotection gave 2-aryl-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidin-4-ones, aza analogues of the known inhibitor XAV939. Introduction of the ring-N in the arylnaphthyridinones and the arylpyridopyrimidinones caused >1000-fold loss in activity, compared with their carbocyclic isoquinolinone and quinazolinone analogues. However, the 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones showed excellent inhibition of the tankyrases, with some examples having IC50 = 2 nM. One compound (7-(4-bromophenyl)-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-one) showed 70-fold selectivity for inhibition of tankyrase-2 versus tankyrase-1. The mode of binding was explored through crystal structures of inhibitors in complex with tankyrase-2.
- Kumpan, Katerina,Nathubhai, Amit,Zhang, Chenlu,Wood, Pauline J.,Lloyd, Matthew D.,Thompson, Andrew S.,Haikarainen, Teemu,Lehti?, Lari,Threadgill, Michael D.
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supporting information
p. 3013 - 3032
(2015/08/03)
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- Diastereoselective nucleophilic cyclopropanation of 1,2-diketones and α-ketoimines with bis(iodozincio)methane
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A reaction of 1,2-diketones and α-ketoimines with bis(iodozincio)methane gave cyclopropan-1,2-diol and 2-aminocyclopropanol respectively via nucleophilic [2+1]cycloaddition. The reaction proceeded via a sequential nucleophilic attack of the dizinc reagent to vicinal two carbonyl group. The reaction showed high diastereoselectivity to give cis-isomer via a face-to-face coordination between the substrate and bis(iodozincio)methane.
- Nomura, Kenichi,Asano, Keisuke,Kurahashi, Takuya,Matsubara, Seijiro
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experimental part
p. 1381 - 1399
(2009/07/17)
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- Multi-Functional Copolymers Comprising Rare Earth Metal Complexes and Devices Thereof
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The invention relates to copolymer complexes of the formula (I): wherein [Ax-[B(C)]y-Dz] denotes a single unit of the copolymer complex that is repeated n times, wherein n is an integer greater than one, and wherein the single unit comprises a conjugated backbone coordinated to a complex (C) comprising rare earth metal(s); x, y and z are numbers greater than zero such that x=y+z; A is independently selected from a group consisting of: fluorene, carbazole, oxadiazole, triphenylamine or derivatives thereof; B is a functional ligand selected from the group consisting of: benzoic acid, 1,3-diphenylpropane-1,3-dione, 1,10-phenanthroline, 2,2-bipyridine, or derivatives thereof; and D is independently selected from a group consisting of: fluorene, carbazole, oxadiazole, triphenylamine or derivatives thereof.
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- Process for preparing vinyl substituted beta-diketones
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A process for preparing vinyl substituted beta-diketones includes reacting a halogen-containing beta-diketone with an olefin in a reaction zone under Heck coupling reaction conditions in the presence of a catalyst, a base, and an organic phosphine to provide a vinyl substituted beta-diketone product.
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Page/Page column 7
(2008/06/13)
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- Synthesis of vinyl-substituted β-diketones for polymerizable metal complexes
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Polymerizable β-diketones for application to metal ion coordination have been prepared and characterized. Bromine-substituted β-diketones were synthesized under Claisen-Schmidt-type condensation conditions. Vinyl groups were substituted for the halide by
- Southard, Glen E.,Murray, George M.
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p. 9036 - 9039
(2007/10/03)
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- Organic light-emitting diodes and related hole transport compounds
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New organic light-emitting diodes and related hole transport compounds and methods for fabrication, using siloxane self-assembly techniques.
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Page/Page column 10
(2010/02/14)
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- Enantioselective borohydride reduction catalyzed by optically active cobalt complexes
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The highly enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing the appropriate alcohol as modifiers and a suitable β-ketoiminato ligand of the catalyst. The enantioselective borohydride reduction has been successfully applied to the preparation of optically active 1,3-diols, the stereoselective reduction of diacylferrocenes, and dynamic and/or kinetic resolution of 1,3-dicarbonyl compounds.
- Yamada, Tohru,Nagata, Takushi,Sugi, Kiyoaki D.,Yorozu, Kiyotaka,Ikeno, Taketo,Ohtsuka, Yuhki,Miyazaki, Daichi,Mukaiyama, Teruaki
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p. 4485 - 4509
(2007/10/03)
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- New Dithio-bis-(diaroylmethanes) and Acetyl Diaroylchloromethyl Bisulfides: Attractive Synthons and Precursors for the Liberation of Highly Reactive Dithiiranes or Thiosulfines
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In a new, feasible procedure five symmetrical para-substituted diaroylmethanes ((4-X-C6H4-CO)2-CH2; X = F, Cl, Br, CH3, and CH3O) are prepared, in most cases in very good yields. For purification and activation, they are converted into the copper(II) complexes of their enolates. Subsequently, three reaction steps with disulfur dichloride (S2Cl2), chlorine, and ethanethioic acid yield new CH-acidic dithio-bis-(diaroylmethanes), α-chlorosulfenic acid chlorides, and acetyl diaroylchloromethyl disulfides. The latter compounds are of interest for the liberation of highly reactive dithiirane/thiosulfine species. With thiomorpholine, α-chlorosulfenic acid chlorides give α-chlorosulfenic acid amides.
- Franek
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p. 895 - 907
(2007/10/03)
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- Synthesis and antifungal activity of 1,3-bis(4-methyl/4-bromo/3-nitrophenyl) propan-1,3-diones and their 2 analogs
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The reaction of substituted acetophenones (1-3) with 4-methyl-, 4-bromo- or 3-nitrobenzaldehyde (4-6) in ethanolic NaOH gives the correponding 1,3-bis(4-methyl/4-bromo/3-nitrophenyl)-2-propen-1-ones (7-9) in good yields, which on bromination yield substit
- Suman, Mrs.,Singh, Rajvir,Malik, M. S.,Kathpal, T. S.,Malik, O. P.
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p. 743 - 746
(2007/10/03)
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- Synthesis of dibenzoylmethane derivatives and inhibition of mutagenicity in Salmonella typhimurium
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Twenty dibenzoylmethanes with methyl, methoxy, bromo, chloro, or fluoro substitution on either one or both benzene rings were synthesized and assayed for inhibition of the mutagenicity of 2-nitrofluorene in S. typhimurium TA98. 2,2-Dimethoxy, 3,3-dimethoxy and 3,3,4,4-tetramethoxydibenzoylmethane was as active as dibenzoylmethane. None of the halogen-substituted dibenzoylmethanes were active. These results demonstrate that dibenzoylmethanes can inhibit the mutagenicity of 2-nitrofluorene, and that modifications made on the benzene rings of dibenzoylmethane cannot enhance the antimutagenicity of this parent compound.
- Choshi,horimoto,Wang,Nagase,Ichikawa,Sugino,Hibino
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p. 1047 - 1049
(2007/10/02)
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