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The molecular design of photo-curable and high-strength benzoxazine for 3D printing
Low viscosity photo-curable benzoxazines (BZs) are designed and synthesized for use in stereolithography 3D printing. An initial investigation shows that the thermally polymerized polybenzoxazines (PBZs) have remarkably highTg(264 °C) and flexural modulus (4.91 GPa) values. Subsequently, the formulated photoprintable resins are employed for use in high-resolution projection micro-stereolithography (PμSL) printing. Complex PBZ 3D structures can be achieved from the as-printed objects after they are thermally treated. These findings advance the design of BZ monomers for photopolymerization-based 3D printing and offer a method for the efficient fabrication of high-performance thermosets for various demanding engineering applications.
Lu, Yong,Ng, Kok Wei Joseph,Chen, Hui,Chen, Xuelong,Lim, Song Kiat Jacob,Yan, Weili,Hu, Xiao
supporting information
p. 3375 - 3378
(2021/04/07)

Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent-Based Switch in Stereopreference
The substrate scope of the asymmetric allylation with zinc organyls catalyzed by 3,3-bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) has been extended to non-cyclic ester organozinc reagents and ketones. Tertiary chiral alcohols are obtained with ee's up to 94% and two stereogenic centers can be created. Compared to the previous lactone reagent the stereopreference switches almost completely, proving the fact that the nature of the organometallic compound is of immense importance for the asymmetry of the product. (Figure presented.).
Lazzarotto, Mattia,Hartmann, Peter,Pletz, Jakob,Belaj, Ferdinand,Kroutil, Wolfgang,Payer, Stefan E.,Fuchs, Michael
supporting information
p. 3138 - 3143
(2021/04/28)

Synthesis and Biological Evaluation of Celastrol Derivatives with Improved Cytotoxic Selectivity and Antitumor Activities
Cdc37 associates kinase clients to Hsp90 and promotes the development of cancers. Celastrol, a natural friedelane triterpenoid, can disrupt the Hsp90-Cdc37 interaction to provide antitumor effects. In this study, 31 new celastrol derivatives, 2a - 2d , 3a - 3g , and 4a - 4t , were designed and synthesized, and their Hsp90-Cdc37 disruption activities and antiproliferative activities against cancer cells were evaluated. Among these compounds, 4f , with the highest tumor cell selectivity (15.4-fold), potent Hsp90-Cdc37 disruption activity (IC50= 1.9 μM), and antiproliferative activity against MDA-MB-231 cells (IC50= 0.2 μM), was selected as the lead compound. Further studies demonstrated 4f has strong antitumor activities both in vitro and in vivo through disrupting the Hsp90-Cdc37 interaction and inhibiting angiogenesis. In addition, 4f exhibited less toxicity than celastrol and showed a good pharmacokinetics profile in vivo. These findings suggest that 4f may be a promising candidate for development of new cancer therapies.
Feng, Jia-Hao,He, Qi-Wei,Hou, Ji-Qin,Hu, Xiao-Long,Long, Huan,Wang, Bao-Lin,Wang, Hao,Wang, Quan,Wang, Rong,Ye, Wen-Cai,Zhang, Li-Xin,Zhang, Xiao-Qi
p. 1954 - 1966
(2021/07/20)

Zinc-Catalyzed β-Functionalization of Cyclopropanols via Enolized Homoenolate
We report herein a zinc-catalyzed β-allylation of cyclopropanols with Morita-Baylis-Hillman (MBH) carbonates with retention of the cyclopropane ring. The reaction is promoted by a zinc aminoalkoxide catalyst, affording cyclopropyl-fused α-alkylidene-δ-valerolactone derivatives in moderate to good yields. Mechanistic experiments suggest that the present reaction does not proceed via direct β-C-H cleavage of the cyclopropanol, but involves zinc homoenolate and its enolization to generate a key bis-nucleophilic species. α-Allylation of this "enolized homoenolate"with MBH carbonate would be followed by regeneration of the cyclopropane ring and irreversible lactonization. The enolized homoenolate mechanism has also been proven to allow for β-functionalization with alkylidenemalononitrile as the reaction partner. A sequence of the present reaction and known cyclopropanol transformation provides an opportunity to transform a simple cyclopropanol into α,β- or β,β-difunctionalized ketones.
Sekiguchi, Yoshiya,Yoshikai, Naohiko
supporting information
p. 18400 - 18405
(2021/11/16)

An efficient approach for the synthesis of new (±)-coixspirolactams
Coixspirolactams, spiro[oxindole-γ-lactones], are found in adlay seeds and exhibit anticancer activity. A novel synthetic methodology was developed to enable an easy access to (±)-coixspirolactam A and a large number of new coixspirolactams in excellent overall yields. The exquisite exploitation of formamide reactivity was essential for the construction of oxindole and lactone scaffolds. This journal is
Nascimento, Vinicius R.,Suenaga, Melissa L. S.,Andrade, Leandro H.
supporting information
p. 5458 - 5465
(2020/08/03)

Design, synthesis and 3D-QSAR analysis of novel thiopyranopyrimidine derivatives as potential antitumor agents inhibiting A549 and Hela cancer cells
Four series of thiopyranopyrimidine AZD9291 derivatives containing acrylamide structure were designed, synthesized and evaluated for their antiproliferative activity against A549 and Hela cancer cells. Most of the compounds exhibited excellent antiproliferative activity against A549 cells. Moreover, the compounds with indole ring fluorine substituted exhibited better antiproliferative activity against Hela cells. The most promising compound 23g exhibited excellent enzymatic inhibitory activity and selectivity for EGFRL858R/T790M double mutations. The IC50 value against EGFRL858R/T790M kinase was 16 nM. The compound 23g inhibits selectively against the mutated form of EGFR, with the selectivity more than 125-fold. Furthermore, compound 23g also inhibited A549 cells, Hela cells and H1975 cells proliferation at a low concentration, and the IC50 values were 0.057 μM, 0.104 μM and 0.916 μM, respectively. To further investigate the QSARs of thiopyranopyrimidine derivatives, the CoMFA (q [2] = 0.765, r2 = 0.965) and CoMSIA (q [2] = 0.875, r2 = 0.956) models on Hela cancer cells were established. The generated 3D-QSAR model was validated to be reliable and can be used for further design and optimization of novel and selective EGFR inhibitors.
Zhao, Bingbing,Zhao, Chengwu,Hu, Xiaohan,Xu, Shan,Lan, Zhou,Guo, Yuping,Yang, Zunhua,Zhu, Wufu,Zheng, Pengwu
(2019/11/03)

Development of Benzenesulfonamide Derivatives as Potent Glutathione Transferase Omega-1 Inhibitors
Glutathione transferase omega-1 (GSTO1-1) is an enzyme whose function supports the activation of interleukin (IL)-1β and IL-18 that are implicated in a variety of inflammatory disease states for which small-molecule inhibitors are sought. The potent reactivity of the active-site cysteine has resulted in reported inhibitors that act by covalent labeling. In this study, structure-activity relationship (SAR) elaboration of the reported GSTO1-1 inhibitor C1-27 was undertaken. Compounds were evaluated for inhibitory activity toward purified recombinant GSTO1-1 and for indicators of target engagement in cell-based assays. As covalent inhibitors, the kinact/KI values of selected compounds were determined, as well as in vivo pharmacokinetics analysis. Cocrystal structures of key novel compounds in complex with GSTO1-1 were also solved. This study represents the first application of a biochemical assay for GSTO1-1 to determine kinact/KI values for tested inhibitors and the most extensive set of cell-based data for a GSTO1-1 inhibitor SAR series reported to date. Our research culminated in the discovery of 25, which we propose as the preferred biochemical tool to interrogate cellular responses to GSTO1-1 inhibition.
Xie, Yiyue,Tummala, Padmaja,Oakley, Aaron J.,Deora, Girdhar Singh,Nakano, Yuji,Rooke, Melissa,Cuellar, Matthew E.,Strasser, Jessica M.,Dahlin, Jayme L.,Walters, Michael A.,Casarotto, Marco G.,Board, Philip G.,Baell, Jonathan B.
p. 2894 - 2914
(2020/04/08)

Palladium-catalyzed remote C-H functionalization of 2-aminopyrimidines
A straightforward strategy was developed for the arylation and olefination at the C5-position of the N-(alkyl)pyrimidin-2-amine core with readily available aryl halides and alkenes, respectively. This approach was highly regioselective, and the transformation was achieved based on two different (Pd(ii)/Pd(iv)) and (Pd(0)/Pd(ii)) catalytic cycles.
Das, Animesh,Jana, Akash,Maji, Biplab
supporting information
p. 4284 - 4287
(2020/04/27)

Design, synthesis and agricultural evaluation of derivatives of N-Acyl-N-(m-fluoro-benzyl)-6-amino-coumarin
ABTRACT: This study aims to design and synthesize a series of N-Acyl-N-(m-fluoro- benzyl)-6- amino-coumarins through the principle of active substructure stitching, which are based on the core structure of N-(m-fluoro-benzyl)-6-amino-coumarin. The structures of target compounds e1–e25 have been characterized by 1H NMR, 13C NMR, ESI-MS and elemental analysis. Meanwhile, their agricultural activity have been evaluated in two weeds (Amaranth and Crabgrass) and four widespread noxious pathogens (V.mali, B.cinerea, F.axysporium and C.bacteria). The herbicidal activity results showed that almost all synthetic molecules have a greater impact on the stem system than on the root. Excellent inhibition rates were discovered from compounds e2–e5 and e20–e23 against Amaranth on stems, which were above 58percent(20 mg/L), 68percent(100 mg/L) respectively. Compounds e2 and e21 also exhibited striking inhibition on stems growth of both weeds. Anti-pathogenic activity showed that all the compounds exerted a better inhibitory activity on B.cinerea at 20 ppm compared to control carbendazim. All the heterocyclic substituted compounds (e17–e24, >57percent) made a better influence than the control (54.1percent) at the100 ppm. This research provides promising herbicidal and anti-pathogenic agents that have the better effects and can be potential for further development.
Ding, Yin-hao,Dong, Jing-jing,Feng, Bai-cheng,Hao, Shuang-hong,Jin, Yan,Wei, Yan
supporting information

(2020/08/19)

Macrolactam Synthesis via Ring-Closing Alkene-Alkene Cross-Coupling Reactions
Reported herein is a practical method for macrolactam synthesis via a Rh(III)-catalyzed ring closing alkene-alkene cross-coupling reaction. The reaction proceeded via a Rh-catalyzed alkenyl sp2 C-H activation process, which allows access to macrocyclic molecules of different ring sizes. Macrolactams containing a conjugated diene framework could be easily prepared in high chemoselectivities and Z,E stereoselectivities.
Goh, Jeffrey,Loh, Teck-Peng,Maraswami, Manikantha
supporting information
p. 9724 - 9728
(2020/12/21)

Preparation method of 2,4,6-trimethylbenzoyl chloride and acyl chloride co-production technology
The invention relates to the field of new materials of fine chemicals, in particular to 2,4,6-trimethylbenzoyl chloride (also known as trimesoyl chloride) and an environment-friendly and economical novel preparation process technology for co-producing series acyl chloride products.
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Paragraph 0045-0047

(2020/11/25)

Continuous production method of acrylyl chloride
The invention relates to the field of organic synthesis, and discloses a continuous production method of acrylyl chloride. According to the method, acrylic acid and thionyl chloride are used as raw materials, and are added to a reaction vessel at a molar ratio of 1:(1-1.5), a catalyst and a polymerization inhibitor are added, heating and refluxing are carried out under normal pressure for generation of acrylyl chloride; during the reaction, a rectification column continuously distills off acrylyl chloride produced by the reaction, and then cooling is carried out; during the cooling process, aby-product beta-chloropropionyl chloride generated in the reaction is liquefied and returned to the reaction vessel due to a higher boiling point, and acrylyl chloride is collected; and after refluxing occurs during the reaction, acrylic acid, the polymerization inhibitor and thionyl chloride are continuously added to the reaction vessel, the returned beta-chloropropionyl chloride undergoes a reaction in the presence of a catalyst to form acrylyl chloride, and thus circulating is carried out. The raw materials of the method of the invention are simple and easy to obtain and have low cost, andthe method of the invention can be carried out under normal pressure, the reaction is mild and controllable, and the final product yield and purity are high.
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Paragraph 0033; 0034; 0035; 0036; 0037; 0038; 0039; 0040

(2019/04/18)

Design, synthesis and biological evaluation of AZD9291 derivatives as selective and potent EGFRL858R/T790M inhibitors
Third-generation epidermal growth factor receptor (EGFR)L858R/T790M inhibitors are still the main drugs for the treatment of advanced non-small cell lung cancer (NSCLC), and these drugs have achieved remarkable clinical efficacy. However, there are still many patients suffering from drug-resistant mutations and drug side effects caused by NSCLC. In this study, guided by the molecular simulation, we applied a structure-based drug design strategy (SBDD) and optimized the structure to obtain a series of potent and selective EGFRL858R/T790M inhibitors. The most potent compound 18e demonstrated excellent kinase inhibitory activity and selectivity for EGFRL858R/T790M double mutants and the IC50 value reached nanomolar level. The selectivity of 18e against wild-type EGFR was near to 200-fold. In addition, compound 18e also inhibited H1975 cells proliferation at G2/M phase and induced apoptosis at a concentration of 0.25 μM, which makes it more valuable for potential lung cancer research.
Zhao, Bingbing,Xiao, Zhen,Qi, Jianguo,Luo, Rong,Lan, Zhou,Zhang, Yanzhuo,Hu, Xiaohan,Tang, Qidong,Zheng, Pengwu,Xu, Shan,Zhu, Wufu
p. 367 - 380
(2018/12/13)

Isoalantolactone derivative, pharmaceutical composition and application thereof
The invention relates to an isoalantolactone derivative, a pharmaceutical composition and application thereof, especially use of the isoalantolactone derivative shown as formula (I) or a salt pharmaceutical compound thereof in preparation of adjuvant drugs treating cancer, a pharmaceutical composition containing a therapeutically effective amount of isoalantolactone derivative (I) or its salt anda pharmaceutically acceptable carrier or a composition with other anticancer drugs.
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Paragraph 0014

(2019/02/02)

Photoredox/Cobalt Dual Catalysis for Visible-Light-Mediated Alkene-Alkyne Coupling
Dual photoredox transition-metal catalysis has recently emerged as a powerful tool for making synthetically challenging carbon-carbon bonds under milder reaction conditions. Herein, we report on the visible-light-mediated controlled generation of low-valent cobalt catalyst without the need for a metallic reductant. It enabled C-C bond formation via ene-yne coupling at room temperature. The generality of this dual catalysis is demonstrated via the creation of sizable molecular diversity with the accommodation of several functional groups.
Rai, Pramod,Maji, Kakoli,Maji, Biplab
supporting information
p. 3755 - 3759
(2019/05/24)

PdII/Novel Chiral Cinchona Alkaloid Oxazoline-Catalyzed Enantioselective Oxidative Cyclization of Aromatic Alkenyl Amides
A highly enantioselective PdII-catalyzed aza-Wacker oxidation tandem cyclization of aromatic nitrogen-containing dienes has been achieved in the presence of novel chiral cinchona alkaloid oxazoline ligands for the first time, affording chiral dihydroindole nitrogen-containing polycyclic compounds with good yields (up to 83 %), high diastereoselectivities (> 95:5 dr), and excellent enantioselectivities (up to 97 % ee).
Tian, Qinqin,Liu, Yulong,Wang, Xiaoyun,Wang, Xie,He, Wei
supporting information
p. 3850 - 3855
(2019/06/08)

Structure-Based Design of Selective, Covalent G Protein-Coupled Receptor Kinase 5 Inhibitors
The ability of G protein-coupled receptor (GPCR) kinases (GRKs) to regulate desensitization of GPCRs has made GRK2 and GRK5 attractive targets for treating heart failure and other diseases such as cancer. Although advances have been made toward developing inhibitors that are selective for GRK2, there have been far fewer reports of GRK5 selective compounds. Herein, we describe the development of GRK5 subfamily selective inhibitors, 5 and 16d that covalently interact with a nonconserved cysteine (Cys474) unique to this subfamily. Compounds 5 and 16d feature a highly amenable pyrrolopyrimidine scaffold that affords high nanomolar to low micromolar activity that can be easily modified with Michael acceptors with various reactivities and geometries. Our work thereby establishes a new pathway toward further development of subfamily selective GRK inhibitors and establishes Cys474 as a new and useful covalent handle in GRK5 drug discovery.
Rowlands, Rachel A.,Cato, M. Claire,Waldschmidt, Helen V.,Bouley, Renee A.,Chen, Qiuyan,Avramova, Larisa,Larsen, Scott D.,Tesmer, John J. G.,White, Andrew D.
supporting information
p. 1628 - 1634
(2019/12/03)

Atom- and Mass-economical Continuous Flow Production of 3-Chloropropionyl Chloride and its Subsequent Amidation
3-Chloropropionyl chloride is a chemically versatile building block with applications in the field of adhesives, pharmaceuticals, herbicides and fungicides. Its current production entails problems concerning safety, prolonged reaction times and the use of excessive amounts of chlorinating reagents. We developed a continuous flow procedure for acid chloride formation from acrylic acid and a consecutive 1,4-addition of hydrogen chloride generating 3-chloropropionyl chloride, as presented in this paper. Up to 94 % conversion was reached in 25 minutes at mild temperatures and pressures. This continuous flow method offers a safer alternative and is highly efficient in terms of consumption of starting product and shorter residence time. Valorization of this building block is exemplified by the synthesis of beclamide, a compound with sedative and anticonvulsant properties. Over 80 % conversion towards this drug was achieved in 1 minute in a continuous flow setup. Further research is needed to telescope the synthesis of 3-chloropropionyl chloride and subsequent beclamide formation without intermediate purification.
Movsisyan, Marine,Heugebaert, Thomas S. A.,Roman, Bart I.,Dams, Rudolf,Van Campenhout, Rudy,Conradi, Matthias,Stevens, Christian V.
supporting information
p. 11779 - 11784
(2018/08/01)

Polymerizable compound, preparation method thereof and display device
The invention provides a polymerizable compound, a preparation method thereof and a display device and relates to the field of liquid crystal display. The polymerizable compound is suitable for use asa reactive mesocrystal and is used for increasing the response speed of a liquid crystal molecule in a liquid crystal medium in which a polymer is stably oriented. The polymerizable compound has a structural general formula as shown in the specification. The invention relates to an application of the polymerizable compound to the liquid crystal medium.
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Paragraph 0106; 0110

(2018/06/26)

Macrolide Synthesis through Intramolecular Oxidative Cross-Coupling of Alkenes
A RhIII-catalyzed intramolecular oxidative cross-coupling between double bonds for the synthesis of macrolides is described. Under the optimized reaction conditions, macrocycles containing a diene moiety can be formed in reasonable yields and with excellent chemo- and stereoselectivity. This method provides an efficient approach to synthesize macrocyclic compounds containing a 1,3-conjugated diene structure.
Jiang, Bing,Zhao, Meng,Li, Shu-Sen,Xu, Yun-He,Loh, Teck-Peng
supporting information
p. 555 - 559
(2018/02/21)

Design, synthesis, antiproliferative activity and docking studies of quinazoline derivatives bearing 2,3-dihydro-indole or 1,2,3,4-tetrahydroquinoline as potential EGFR inhibitors
Eight series of quinazoline derivatives bearing 2,3-dihydro-indole or 1,2,3,4-tetrahydroquinoline were designed, synthesized and evaluated for the IC50 values against three cancer cell lines (A549, MCF-7 and PC-3). Most of the forty nine target compounds showed excellent antiproliferative activity against one or several cancer cell lines. The compound 13a showed the best activity against A549, MCF-7 and PC-3 cancer cell lines, with the IC50 values of 1.09 ± 0.04 μM, 1.34 ± 0.13 μM and 1.23 ± 0.09 μM, respectively. Eight selected compounds were further selected to evaluated for the inhibitory activity against EGFR kinase. Three of them showed equal activity against EGFR kinase to positive control afatinib. AnnexinV-FITC, propidium iodide (PI) double staining and acridine orange single staining results indicated that the compound 13a could induce apoptosis of human lung cancer A549 cells.
OuYang, Yiqiang,Zou, Wensheng,Peng, Liang,Yang, Zunhua,Tang, Qidong,Chen, Mengzi,Jia, Shuang,Zhang, Hong,Lan, Zhou,Zheng, Pengwu,Zhu, Wufu
p. 29 - 43
(2018/05/24)

Palladium-Catalyzed H/D Exchange Reaction with 8-Aminoquinoline as the Directing Group: Access to ortho-Selective Deuterated Aromatic Acids and β-Selective Deuterated Aliphatic Acids
We develop a palladium-catalyzed H/D exchange reaction with 8-aminoquinoline as the directing group as well as D2O as the source of deuterium atom and solvent. This reaction achieves selectively H/D exchange at the ortho-C-H of aromatic amides and the β-C-H of aliphatic amide. Ortho-deuterated aromatic acids and β-deuterated aliphatic acids are obtained by removal of the directing group. And a possible mechanism is also proposed.
Zhao, Donghong,Luo, Haofan,Chen, Binhui,Chen, Wenteng,Zhang, Guolin,Yu, Yongping
p. 7860 - 7866
(2018/07/21)

A 2, 3 - two bromine propionyl chlorides production process (by machine translation)
The present invention relates to the field of producing chemical products, especially 2, 3 - two bromine propionyl chlorides production field. 2. 3 - two bromine propionyl chlorides is an important chemical raw materials. Currently in production have different production process. The process flow includes: 1, addition; 2, distillation. (by machine translation)
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Paragraph 0007

(2017/08/28)

A method for synthesis of acryloyl chloride
The invention discloses a synthetic method of acryloyl chloride. Triphosgene reacts with acrylic acid to produce the acryloyl chloride. The triphosgene and the acrylic acid are used as raw materials, and one of dichloromethane, chloroform, acetone, ethyl ether, benzene, tetrahydrofuran, n-hexane, cyclohexane and the like is used as an organic solvent; one of hydroquinone, resorcinol, cupper chloride and a mixture of tin tetrachloride and hydroquinone is used as an acrylic acid polymerization inhibitor, the triphosgene is firstly dissolved in the organic solvent, then the organic solvent is added to a reactor containing the polymerization inhibitor, an organic nitrogen compound and the acrylic acid for reaction at the temperature of 70 DEG C for 9-38 h, and the high-yield acryloyl chloride can be obtained. The reaction is high in conversion rate which is about 99%, no other by-product is produced, the reaction condition is mild, and materials can be directly fed for the next reaction without separation.
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Paragraph 0006; 0021-0022

(2017/02/23)

N-substituted acrylamide monomer and preparation method thereof, and acrylamide copolymer and preparation method thereof
The invention belongs to the field of oilfield chemical agents and especially relates to an N-substituted acrylamide monomer and a preparation method thereof, and an acrylamide copolymer and a preparation method thereof. The N-substituted acrylamide monomer has the structure as the formula (I), wherein R1 and R2 are independently selected from alkyl groups. The acrylamide copolymer with the N-substituted acrylamide monomer has excellent temperature and salt resistances and has high viscosity even under high temperature and high salt conditions. A test result proves that the acrylamide copolymer prepared by copolymerizing the N-substituted acrylamide monomer with acrylamide is higher than 40 mPa*s under the high temperature and high salt conditions (test temperature is 85 DEG C, solvent total dissolved solid is 45000 water, total concentration of Ca and Mg is 1800 mg/L, and target liquid concentration is 2000 mg/L).
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Paragraph 0097; 0098; 0099; 0100

(2016/10/10)

A biphenyl type acrylate liquid crystal resin synthesis method
The invention discloses biphenyl acrylate liquid crystal resin and a synthetic method thereof. The synthetic method comprises the steps of synthesizing symmetrical and unsaturated liquid crystal resin through an acylation reaction and an esterification reaction by using unsaturated double bonds of acrylic acid; preparing di-ester and biphenyl liquid crystal resin by using the characteristics of 3,3',5,5'-tera-alkyl (or fluoro) biphenol, such as strong rigidity, large intermolecular attraction and conjugation effect of benzene rings. The biphenyl acrylate liquid crystal resin disclosed by the invention has the characteristics of the biphenyl liquid crystal resin, such as no color, generally relatively high clearing point, ultra-high dielectric anisotropy value, good physical and chemical properties, good optical and chemical stability, anisotropy, very wide liquid crystal phase region, adjustable viscosity, birefringence and physical parameters, good molding processing property and the like.
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Paragraph 0028; 0029; 0034; 0035; 0040; 0041; 0046; 0047

(2019/02/02)

A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
p. 420 - 430
(2015/12/31)

Rhodium(III)-Catalyzed Cascade Cyclization/Electrophilic Amidation for the Synthesis of 3-Amidoindoles and 3-Amidofurans
A rhodium(III)-catalyzed cascade cyclization/electrophilic amidation using N-pivaloyloxylamides as the electrophilic nitrogen source has been developed. This protocol provides an efficient route for the synthesis of 3-amidoindoles and 3-amidofurans under mild conditions with good functional group tolerance. The synthetic utility of this reaction has been demonstrated through the derivatization of the 3-amidoindoles to several heterocycle-fused indoles.
Hu, Zhiyong,Tong, Xiaofeng,Liu, Guixia
supporting information
p. 2058 - 2061
(2016/06/01)

Facile synthesis of fluorovinyl-containing lactams via ring-closing metathesis of N-substituted 2-fluoroallylamides
A cost-efficient method for the preparation of a series of N-substituted 2-fluoroallylamines and their application in the synthesis of fluoroalkene-containing lactams are described. N-substituted 2-fluoroallylamine could be readily synthesized from methyl 2-fluoroacrylate via aminolysis and subsequently selective reduction of the amide group. These amines were further converted into the corresponding amides with diverse acids bearing a terminal double bond. The Ring-Closing Metathesis (RCM) of the resulting amides led to the formation fluorovinyl-containing lactams in good yields.
Li, Yang,Li, Kai,Wu, Yue,Ma, Qiaoning,Lei, Xinsheng
p. 4845 - 4853
(2016/07/18)

A PROCESS FOR THE PREPARATION OF IBRUTINIB
The present invention provides processes for the preparation of ibrutinib, intermediate compounds of Formula VI and Formula VIII, and salts thereof. The processes of the present invention are commercially viable, cost-effective, environmentally friendly, and make use of inexpensive, non-hazardous, safe chemicals that are easy to handle.
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Page/Page column 27; 28

(2016/06/15)

Magnetic Co(II) porphyrin nanospheres appending different substituent groups showing higher catalytic activities in cyclohexane
Magnetic polymer nanospheres immobilizing Co(II) porphyrins with different substituents were prepared and exhibited satisfying size, morphology and magnetic responsiveness. These core/shell structured nanospheres showed much higher catalytic activities in hydroxylating cyclohexane than the non-supported Co(II) porphyrin analogues. Moreover, these magnetic nanospheres could be easily recovered and reused for up to five times with maintaining their high catalytic efficiencies, and thus are good candidates for high-efficient, environmental-friendly catalysts.
Zhao, Ping,Liu, Min-Chao,Zheng, Min,Jin, Shu-Fang,Tang, Ding-Tong,Lin, Jia-Qi,Ma, Yan-Na,Chen, Jiong,Liu, Hong-Jian
p. 9843 - 9850
(2016/08/31)

A PROCESS FOR THE PREPARATION OF IBRUTINIB
The present invention provides a process for the preparation of ibrutinib of Formula I.
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Page/Page column 15

(2016/10/11)

Regiocontrolled Coupling of Aromatic and Vinylic Amides with α-Allenols to Form γ-Lactams via Rhodium(III)-Catalyzed C-H Activation
A mild, regiocontrolled coupling of aromatic and vinylic amides with α-allenols to form γ-lactams via rhodium(III)-catalyzed C-H activation has been demonstrated. This [4 + 1] annulation reaction provides an efficient method for the synthesis of isoindolinones and 1,5-dihydro-pyrrol-2-ones bearing a tetrasubstituted carbon atom α to the nitrogen atom with good functional group tolerance. The hydroxyl group in the allene substrate is essential in controlling the chemo- and regioselectivity of the reaction probably by coordination interaction with the rhodium catalyst.
Zhou, Zhi,Liu, Guixia,Lu, Xiyan
supporting information
p. 5668 - 5671
(2016/11/17)

Safe, selective, and high-yielding synthesis of acryloyl chloride in a continuous-flow system
Acid chlorides are an important class of compounds and their high reactivity and instability has prompted us to develop a straightforward procedure for their synthesis with ondemand and on-site synthesis possibilities. The focus of this report is acryloyl chloride, mainly important for the acrylate and polymer industry. A continuous-flow methodology was developed for the fast and selective synthesis of the otherwise highly unstable acryloyl chloride. Three routes were investigated in a microreactor setup and all three can potentially be used for its production. The methodology was further expanded to the synthesis of other unstable acid chlorides by both the thionyl chloride and the oxalyl chloride mediated processes. The most sustainable method was the oxalyl chloride mediated procedure under solvent-free conditions, in which nearequimolar amounts of carboxylic acid and oxalyl chloride were used in the presence of catalytic amounts of DMF at room temperature. Within 1 to 3 min, nearly full conversions into the acid chlorides were achieved.
Movsisyan, Marine,Heugebaert, Thomas S. A.,Dams, Rudy,Stevens, Christian V.
p. 1945 - 1952
(2018/08/17)

Negative-type photosensitive resin composition, pattern forming method, cured film, insulating film, color filter, and display device
A negative-type photosensitive resin composition capable of forming a pattern having favorable adhesiveness at a low light exposure; a pattern forming method using the resin composition; a cured film, an insulating film, a color filter formed using resin composition; and a display device provided with the cured film, insulating film, or color filter. The resin composition contains a compound represented by the following formula (1). In the formula, R1 and R2 each independently indicate a hydrogen atom or an organic group, but at least one indicates an organic group. R1 and R2 may be bonded to form a ring structure and may contain a hetero atom bond. R3 indicates a single bond or an organic group. R4 to R9 each independently indicate a hydrogen atom, an organic group, etc., but R6 and R7 are never hydroxyl groups. R10 indicates a hydrogen atom or an organic group.
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(2016/02/12)

Modified chitosan for the collection of reactive blue 4, arsenic and mercury from aqueous media
In the present investigation a series of modified chitosan as adsorbents were synthesized free radically at 70°C using acryloylated chitosan (AC-chitosan) as macromer, 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS), 2-(diethylamino) ethylmethacrylate (DAEMA) as co-monomers and N,N'-methylenebisacrylamide (N-MBA) as a crosslinker for using as adsorbents in effluent remediation. Their structures(1H and13C NMR), thermal stability (TG/DTG), surface morphology (SEM), reactive blue 4 (RB4), toxicmetals such as arsenic (AsO2-) and mercury (Hg2+) uptake, swellability and reusability were evaluated.The adsorption of RB4 (701 mg/g), and the uptake of AsO2- (551 mg/g) and Hg2+ (455 mg/g) showed Lang-muir isotherm behavior with pseudo-first-order kinetics. The diffusion of water, RB4, AsO2- and Hg2+ into the matrix followed non-Fickian mechanism. The evaluated changes in Gibbs free energy (δG°), entropy(δS°) and enthalpy (δH°) for adsorption indicated that the process was exothermic..
Dhanapal,Subramanian
p. 123 - 132
(2015/02/19)

Synthesis, characterization and ionic conductivity of supramolecular structure of uracil-functionalized PEG/LiClO4 blend system
In this paper, the synthesis and ionic conductivity behaviour of supramolecular structure based end group functionalized poly(ethylene glycol) with uracil are reported. The uracil (U) functionalized poly(ethylene glycol) (PEG), (U-PEG-U) was synthesised through Michael addition. The synthesized polymer electrolyte was characterized by Fourier-transform infrared and nuclear magnetic resonance spectral methods. Further, we described the interaction behaviour of synthesized polymer electrolyte with Li+ ions. Differential scanning calometry and FTIR studies demonstrates that the significant ability of functionalized poly(ethylene glycol) to donate its electron to coordinate with lithium ion. It is further observed that the ionic conductivity of polymer electrolyte is not only dependent on the electron donation strength of carbonyl group, but also on the molecular structure of polyester.
Rajendran,Jaisankar
p. 646 - 648
(2015/01/30)

Palladium-Catalyzed Heck-type Domino Cyclization and Carboxylation to Synthesize Carboxylic Acids by Utilizing Chloroform as the Carbon Monoxide Source
A palladium-catalyzed domino cyclization and carboxylation reaction for synthesis of a variety of carboxylic acids was developed, where chloroform was used as "carbon monoxide" source. The in situ generated neopentylpalladium species by Heck cyclization was efficiently trapped by dichlorocarbene to form a series of carboxylic acids. It was found that in this type of domino reaction CHCl3 is a convenient and safe alternation for CO gas.
Liu, Xianglei,Li, Bin,Gu, Zhenhua
p. 7547 - 7554
(2015/08/18)

Continuous recycling of homogeneous Pd/Cu catalysts for cross-coupling reactions
Given the importance of homogeneous catalysts recycling in organic chemistry, we have developed a unique microfluidic loop system for automated continuous recirculation of a soluble polymer supported metal catalyst for novel isocyanide cross-coupling reactions under thermomorphic multicomponent solvent (TMS) conditions. Our system provides an innovative approach for the chemical library synthesis of quinazolinone derivatives as well as an important intermediate of Merck's LTD4 antagonist "Singulair" with efficient continuous homogeneous catalyst recycling.
Sharma, Siddharth,Basavaraju,Singh, Ajay K.,Kim, Dong-Pyo
supporting information
p. 3974 - 3977
(2014/08/18)

Phenylboronate-diol crosslinked glycopolymeric nanocarriers for insulin delivery at physiological pH
Research into polymers with glucose-sensitivity in physiological conditions has expanded recently due to their therapeutic potential in diabetes. Herein, to explore the glucose-responsive properties of a new polymer under physiological conditions, we synthesized an amphiphilic block glycopolymer based on phenylboronic acid and a carbohydrate, which was named poly(d- gluconamidoethyl methacrylate-block-3-acrylamidophenylboronic acid) (p(AAPBA-b-GAMA)). Based on the cross-linking between the diol groups of the carbohydrates and phenylboronic acid, the glycopolymers self-assembled to form nanoparticles (NPs). The glucose-sensitivity was revealed by the swelling behavior of the NPs at different glucose concentrations and was found to be dependent on the glucose level. The morphology of the NPs revealed by transmission electron microscopy showed that the NPs were spherical in shape with good dispersity. The cell viability of the NPs investigated by MTT assay was more than 90%, indicating that the glycopolymers had good cytocompatibility. Insulin could be loaded onto the glycopolymer NPs with high efficiency (up to 10%), and insulin release increased with enhancement of the glucose level in the medium. Such a glucose-responsive glycopolymer is an excellent candidate that holds great potential in the treatment of diabetes.
Guo, Qianqian,Wu, Zhongming,Zhang, Xinge,Sun, Lei,Li, Chaoxing
p. 911 - 920
(2014/02/14)

DEUTERATED IBRUTINIB
The present invention in one embodiment provides a compound of Formula (I); or a pharmaceutically acceptable salt thereof, wherein the variables shown in Formula (I) are as defined in the specification.
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Paragraph 103; 110; 111

(2014/02/16)

Highly chemo-, regio-, and enantioselective rhodium-catalyzed cross-cyclotrimerization of two different alkynes with alkenes
It has been established that a cationic rhodium(I)/(R)-tol-binap complex catalyzes the cross-cyclotrimerization of silylacetylenes, di-tert-butyl acetylenedicarboxylates, and acrylamides with excellent chemo-, regio-, and enantioselectivities. Unsymmetrical alkynoates can also be employed in place of di-tert-butyl acetylenedicarboxylate for this process, but with reduced chemoselectivity. Cross-training: It has been established that a cationic rhodium(I)/(R)-tol-binap complex catalyzes the cross-cyclotrimerization of silylacetylenes, di-tert-butyl acetylenedicarboxylates, and acrylamides with excellent chemo-, regio-, and enantioselectivities. Unsymmetrical alkynoates can also be employed in place of di-tert-butyl acetylenedicarboxylate for this process, but with a reduced chemoselectivity.
Hara, Jun,Ishida, Mana,Kobayashi, Masayuki,Noguchi, Keiichi,Tanaka, Ken
supporting information
p. 2956 - 2959
(2014/04/03)

Synthesis and binding profile of haloperidol-based bivalent ligands targeting dopamine D2-like receptors
Homodimers of dopamine D2-like receptors are suggested to be of particular importance in the pathophysiology of schizophrenia and, thus, serve as promising targets for the discovery of atypical antipsychotics. This study describes the development of a series of novel bivalent molecules with a pharmacophore derived from the dopamine receptor antagonist haloperidol. These dimers were investigated in comparison to their monomeric analogues for their D2long, D2short, D3, and D4 receptor binding and the ability to bridge two neighboring receptor protomers. Radioligand binding studies provided diagnostic insights when Hill slopes close to two for the bivalent ligand 13 incorporating 22 spacer atoms and a comparative analysis with monovalent control ligands indicated a bivalent binding mode with a simultaneous occupancy of two neighboring binding sites.
Salama, Ismail,L?ber, Stefan,Hübner, Harald,Gmeiner, Peter
supporting information
p. 3753 - 3756
(2014/09/16)

Synthesis of sulfonated cholesterol derivatives - Electrical, thermal, and optical properties
Poly(cholesterylacrylatesulfone) (PCHAS) and poly(cholesterylacrylatesulfone-co-1-hexene)s (PCHASHs) at different ratios are synthesized from the monomer cholesteryl acrylate. The liquid crystalline phases are observed under a hot stage fitted with a polarizing optical microscope. The polysulfone and copolysulfones are characterized by FT-IR, 1H-NMR, DSC, and TGA techniques. From SEM (EDX) the qualitative amounts of elemental sulfur found in PCHAS and PCHASH11 are 2.90 weights (%) and 4.39 weights (%), respectively. The GPC data using THF as the solvent shows that the number average molecular weight of the PCHAS is 5268 g/mol and the molecular weights of the PCHASHs are higher than the PCHAS. Copyright Taylor & Francis Group, LLC.
Hoque, Samiul,Dass, Narendra Nath,Bhattacharyya, Krishna Gopal,Sarma, Neelotpal Sen
p. 149 - 162
(2014/05/20)

Synthesis and biological evaluation of 2-substituted quinoline 6-carboxamides as potential mGluR1 antagonists for the treatment of neuropathic pain
A series of 2-amino and 2-methoxy quinoline-6-carboxamide derivatives have been synthesized and their metabotropic glutamate receptor type 1 (mGluR1) antagonistic activities were evaluated in a functional cell-based assay. The compound 13c showed the highest potency with IC50 value of 2.16μM against mGluR1. Finally, in vivo evaluation of 13c in the rat spinal nerve ligation (SNL) model exhibited weak analgesic effects with regard to both mechanical allodynia and cold allodynia.
Kim, Younghee,Son, Jiwon,Kim, Juhyeon,Baek, Du-Jong,Lee, Yong Sup,Lim, Eun Jeong,Lee, Jae Kyun,Pae, Ae Nim,Min, Sun-Joon,Cho, Yong Seo
p. 508 - 518
(2014/07/08)

Enantioselective synthesis of amaryllidaceae alkaloids (+)-vittatine, (+)-epi-vittatine, and (+)-buphanisine
Cat. on a hot tin roof: Enantioselective catalytic Michael addition of α-cyanoketones to acrylates under bifunctional organocatalysis was used to construct the unique arylic all-carbon quaternary stereocenter, which is synthetically crucial in the chemical synthesis of optically pure cis-aryl hydroindole alkaloids. The protocol offers an asymmetric route to (+)-vittatine, (+)-epi-vittatine, and (+)-buphanisine. Copyright
Wei, Meng-Xue,Wang, Cheng-Tao,Du, Ji-Yuan,Qu, Hu,Yin, Pei-Rong,Bao, Xu,Ma, Xiao-Yan,Zhao, Xian-He,Zhang, Guo-Biao,Fan, Chun-An
supporting information
p. 1966 - 1971
(2013/09/23)

Rh(III)-catalyzed halogenation of vinylic C-H bonds: Rapid and general access to Z-halo acrylamides
Herein, the regio- and stereoselective iodination, along with some examples for the bromination, of readily available acrylamides to access a variety of differently substituted Z-haloacrylic acid derivatives is reported. The reaction proceeds under mild conditions via a Rh(III)-catalyzed C-H-activation/ halogenation mechanism and represents a rare example of a direct halogenation of electron-poor acrylic acid derivatives.
Kuhl, Nadine,Schroeder, Nils,Glorius, Frank
supporting information
p. 3860 - 3863
(2013/09/02)

Photo-initiated thiol-ene "click" hydrogels from RAFT-synthesized poly(N-isopropylacrylamide)
Despite the efficiency and robustness of the widely used copper-catalyzed 1,3-dipolar cycloaddition reaction, the use of copper as a catalyst is often not attractive, particularly for materials intended for biological systems. The use of photo-initiated thiol-ene as an alternative "click" reaction to synthesize "model networks" is investigated here. Poly(N- isopropylacrylamide) precursors were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and were designed to have trithiocarbonate moieties as end groups. This structure design provides opportunity for subsequent end-group modifications in preparation for thiol-ene "click." Two reaction routes have been proposed and studied to yield thiol and ene moieties. The advantages and disadvantages of each reaction path were investigated to propose a simple but efficient route to prepare copper-free "click" hydrogels.
Ooi, Huey Wen,Jack, Kevin S.,Whittaker, Andrew K.,Peng, Hui
p. 4626 - 4636
(2013/10/21)

A fluorescein-based probe with high selectivity to cysteine over homocysteine and glutathione
A fluorescent probe based on fluorescein displays excellent selectivity and sensitivity for cysteine and its application for bio-imaging is described.
Wang, Huilin,Zhou, Guodong,Gai, Hongwei,Chen, Xiaoqiang
supporting information
p. 8341 - 8343
(2012/10/29)

Total synthesis of (+)-trans-trikentrin A
Several syntheses have already been reported for cis-trikentrins and herbindoles, which are indole alkaloids unsubstituted at the C2 and C3 positions that bear a trans-1,3-dimethylcyclopentyl unit. Herein, we describe the first asymmetric and stereoselective synthesis of the more challenging trans-trikentrin A as its naturally occurring isomer. Different approaches were investigated and the strategy of choice was a combination of an enzymatic kinetic resolution and a thallium(III)-mediated ring contraction. The antiproliferative activities of the natural product and related intermediates have been tested against human tumor cell lines, leading to the discovery of new compounds with potent antitumor activity. Simple target? Take a look again! The first stereoselective synthesis of a trans-trikentrin is described (see scheme). In contrast, all cis-related natural products have already been synthesized. An enzymatic kinetic resolution and a ring contraction are the key steps. Potent antitumor compounds have been discovered during this study. Copyright
Tébéka, Iris R. M.,Longato, Giovanna B.,Craveiro, Marcus V.,De Carvalho, Jo?o E.,Ruiz, Ana L. T. G.,Silva Jr., Luiz F.
supporting information
p. 16890 - 16901
(2013/03/14)