- Transition-metal-free and facile synthesis of 3-alkynylpyrrole-2,4-dicarboxylates from methylene isocyanides and propiolaldehyde
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A transition-metal-free, facile and efficient method for the synthesis of 3-alkynylpyrrole-2,4-dicarboxylates from methylene isocyanides and propiolaldehyde with moderate to good yields has been developed. The direct transformation process and good tolerance of various substituents make it an alternative approach to previous protocols, and potential applications of these investigated compounds are expected with or without post-modifications.
- Chen, Xiaojuan,Fu, Liping,Huo, Xiaoli,Shao, Jiaan,Yu, Liya,Zeng, Linghui,Zhang, Chong,Zhang, Jiankang,Zhu, Huajian
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supporting information
p. 16430 - 16433
(2021/10/01)
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- Compound as protein degradation agent and preparation method and medical application thereof
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The invention discloses a compound serving as a protein degrading agent and a preparation method and medical application thereof, and particularly discloses a compound represented by the formula (I) and a pharmaceutically acceptable salt thereof, and the
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Paragraph 0254-0257
(2021/11/03)
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- Mimics of Pincer Ligands: An Accessible Phosphine-Free N-(Pyrimidin-2-yl)-1,2-azole-3-carboxamide Framework for Binuclear Pd(II) Complexes and High-Turnover Catalysis in Water
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We report for the first time cyclic phosphine-free "head to tail"N,N,N pincer-like (pincer complexes mimicking) N-(pyrimidin-2-yl)-1,2-azole-3-carboxamide Pd(II) complexes with deprotonated amide groups as high-turnover catalysts (TON up to 106, TOF up to 1.2 × 107 h-1) for cross-coupling reactions on the background of up to quantitative yields under Green Chemistry conditions. The potency of the described catalyst family representatives was demonstrated in Suzuki-Miyaura, Mizoroki-Heck, and Sonogashira reactions on industrially practical examples. Corresponding ligands could be synthesized based on readily available reagents through simple chemical transformations. Within the complex structures, a highly unusual 1,3,5,7-tetraza-2,6-dipalladocane frame could be observed.
- Bumagin, Nikolay A.,Dikusar, Evgenij A.,Ivashkevich, Ludmila S.,Kletskov, Alexey V.,Kolesnik, Iryna A.,Lyakhov, Alexander S.,Petkevich, Sergey K.,Potkin, Vladimir I.
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supporting information
(2020/08/12)
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- Regioselective Iron-Catalysed Cross-Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents
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An iron-catalysed Kumada-type cross-coupling reaction between aryl substituted propargylic bromides and arylmagnesium reagents has been developed. Propargylic coupling products were the main or only outcome, and propargyl/allene regioselectivity was shown to depend on the electronic nature of the substituents on the triple bond of the substrate and on the arylmagnesium halide. Best selectivities were observed when electron donating substituents were present in either reagent. The process is stereoespecific, occurs with configuration inversion and no carbon-based radicals seem to be involved in the mechanism. (Figure presented.).
- Manjón-Mata, Inés,Quirós, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 146 - 151
(2019/12/11)
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- Chemo- And regioselective click reactions through nickel-catalyzed azide-alkyne cycloaddition
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Metal-catalyzed cycloaddition is an expeditious synthetic route to functionalized heterocyclic frameworks. However, achieving reactivity-controlled metal-catalyzed azide-alkyne cycloadditions from competing internal alkynes has been challenging. Herein, we report a nickel-catalyzed [3 + 2] cycloaddition of unsymmetrical alkynes with organic azides to afford functionalized 1,2,3-triazoles with excellent regio- and chemoselectivity control. Terminal alkynes and cyanoalkynes afford 1,5-disubstituted triazoles and 1,4,5-trisubstituted triazoles bearing a 4-cyano substituent, respectively. Thioalkynes and ynamides exhibit inverse regioselectivity compared with terminal alkynes and cyanoalkynes, affording 1,4,5-trisubstituted triazoles with 5-thiol and 5-amide substituents, respectively. Density functional theory calculations are performed for the elucidation of the reaction mechanism. The computed mechanism suggests that a nickellacyclopropene intermediate is generated by the oxidative addition of the alkyne substrate to the Ni(0)-Xantphos catalyst, and the subsequent C-N coupling of this intermediate with an azide is responsible for the chemo- and regioselectivity.
- Baek, Seung-Yeol,Baik, Mu-Hyun,Choe, Wonyoung,Hong, Sung You,Jeon, Ji Hwan,Jeong, Seo Yeong,Kim, Woo Gyum,Nam, Dongsik
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supporting information
p. 3374 - 3381
(2020/05/14)
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- Catalytic Access to Functionalized Allylic gem-Difluorides via Fluorinative Meyer–Schuster-Like Rearrangement
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An unprecedented approach for efficient synthesis of functionalized allylic gem-difluorides via catalytic fluorinative Meyer–Schuster-like rearrangement is disclosed. This transformation proceeded with readily accessible propargylic fluorides, and low-cost B–F reagents and electrophilic reagents by sulfide catalysis. A series of iodinated, brominated, and trifluoromethylthiolated allylic gem-difluorides that were difficult to access by other methods were facilely produced with a wide range of functional groups. Importantly, the obtained iodinated products could be incorporated into different drugs and natural products, and could be expediently converted into many other valuable gem-difluoroalkyl molecules as well. Mechanistic studies revealed that this reaction went through a regioselective fluorination of alkynes followed by a formal 1,3-fluorine migration under the assistance of the B–F reagents to give the desired products.
- An, Rui,Li, Huimin,Liao, Lihao,Wu, Jin-Ji,Xu, Yang,Zhao, Xiaodan
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supporting information
p. 11010 - 11019
(2020/05/18)
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- Catalytic claisen rearrangement by intercepting ketenimines with propargylic alcohols: A strategy to generate and transform ketenimines from radicals
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An efficient strategy for facilitating the cross-coupling of two radicals has been established via the coordination of a radical with a metal catalyst. This strategy provides a remarkable ability to harness the reactivity of nitrile-containing azoalkanes and enables a novel cascade reaction with nitrile-containing azoalkanes and propargylic alcohols to be established. By using this reaction, a range of acetylenic and allenic amides were obtained that provides a versatile platform for further derivatizations.
- Yan, Xuyang,Liu, Hongchi,Wei, Shenquan,Huang, Hanmin
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supporting information
p. 6794 - 6798
(2020/09/15)
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- Catalyst-Free Annulation of 2-Pyridylacetates and Ynals with Molecular Oxygen: An Access to 3-Acylated Indolizines
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A catalyst and additive-free annulation of 2-pyridylacetates and ynals under molecular oxygen was the first developed, affording 3-acylated indolizines in good to excellent yields. Molecular oxygen was used as the source of the carbonyl oxygen atom in indolizines. This approach was compatible with a wide range of functional groups, and especially it has been successfully extended to unsaturated double bonds and triple bonds, which were difficult to prepare by previous methods in a single step.
- Chen, Zhengwang,Liang, Pei,Ma, Xiaoyue,Luo, Haiqing,Xu, Guohai,Liu, Tanggao,Wen, Xiaowei,Zheng, Jing,Ye, Hui
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supporting information
p. 1630 - 1639
(2019/01/26)
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- Metal-free aminothiation of alkynes: Three-component tandem annulation toward indolizine thiones from 2-alkylpyridines, ynals, and elemental sulfur
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A metal-free three-component annulation reaction for the synthesis of indolizine thiones via tandem C-C/C-N/C-S bond formation was developed. Various 2-alkylpyridines with aromatic ynals and elemental sulfur proceeded smoothly under catalyst-free conditions, and the desired products were obtained in moderate to excellent yields.
- Chen, Zhengwang,Liang, Pei,Xu, Fan,Deng, Zhen,Long, Lipeng,Luo, Guotian,Ye, Min
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supporting information
p. 12639 - 12647
(2019/10/11)
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- Palladium-Catalyzed Nitrile-Assisted C(sp3)-Cl Bond Formation for Synthesis of Dichlorides
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A palladium-catalyzed coupling procedure of alkenes with alkynylnitriles has been demonstrated for the synthesis of dichlorides. The reaction is the first example of nitrile-assisted C(sp3)-Cl formation promoted by coordination of a cyano group with an alkylpalladium(II) complex. The construction of a five-membered cycle intermediate successfully inhibits the β-hydride abstraction, resulting in direct C-Cl bond reductive elimination of alkylpalladium(II) chloride.
- He, Dandan,Huang, Liangbin,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 8308 - 8311
(2019/10/16)
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- Catalytic asymmetric synthesis of 2,5-dihydrofurans using synergistic bifunctional Ag catalysis
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We report a bifunctional Ag catalyst promoted intramolecular capture of oxonium ylides with alkynes for the enantioselective synthesis of 2,5-dihydrofurans. This represents unprecedented synergistic catalysis of a bifunctional Ag catalyst. Mechanistic studies revealed that [(R)-3,5-DM-BINAP](AgSbF6)2 (9) is likely to be the active catalytic species and that the reaction involves second order kinetics with respect to 9, suggesting that two molecules of 9 are involved in the intramolecular trapping of a Ag-associated oxonium ylide with a Ag-activated alkyne. Based on our mechanistic hypothesis, we further optimized the reaction, rendering a facile approach to 2,5-dihydrofurans in good to excellent yields in a highly chemo- and enantioselective fashion.
- Shi, Taoda,Teng, Shenghan,Gopi Krishna Reddy, Alavala,Guo, Xin,Zhang, Yueteng,Moore, Kohlson T.,Buckley, Thomas,Mason, Damian J.,Wang, Wei,Chapman, Eli,Hu, Wenhao
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supporting information
p. 8737 - 8744
(2019/10/16)
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- Substituted 1-(isoxazol-3-yl)methyl-1H-1,2,3-triazoles: Synthesis, palladium(II) complexes, and high-turnover catalysis in aqueous media
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New substituted 3-((1H-1,2,3-triazol-1-yl)methyl)-5-arylisoxazoles (aryl = Ph, p-Tol) and 2-(5-phenylisoxazol-3-yl)-5-(2-(1-((5-(p-tolyl)isoxazol-3-yl)methyl)-1H-1,2,3-triazol-4-yl)ethyl)-1,3,4-oxadiazole were synthesized by means of click-chemistry proce
- Bumagin, Nikolay A.,Kletskov, Alexey V.,Petkevich, Sergey K.,Kolesnik, Iryna A.,Lyakhov, Alexander S.,Ivashkevich, Ludmila S.,Baranovsky, Alexander V.,Kurman, Peter V.,Potkin, Vladimir I.
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p. 3578 - 3588
(2018/05/28)
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- Iron-Catalyzed Coupling of Propargyl Bromides and Alkyl Grignard Reagents
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An iron-catalyzed Kumada-type cross-coupling reaction of propargyl halides with alkylmagnesium reagents is described. The reaction is fast, takes place in smooth conditions, tolerates several functional groups that would be able to react with the Grignard reagent, and may afford either allene or propargyl coupling derivatives. Factors involved in the observed regioselectivity have been studied.
- Domingo-Legarda, Pablo,Soler-Yanes, Rita,Quirós-López, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 4900 - 4904
(2018/09/10)
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- Cadmium Metal-Organic Frameworks Based on Ditopic Triazamacrocyclic Linkers: Unusual Structural Features and Selective CO2 Capture
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Two three-dimensional cadmium metal-organic frameworks with general formula [Cd2(L1)(H2O)3](NO3)0.7(HCOO)0.2Br0.1 (Cd2L1, L1 = 1,4,7-tris(4-carboxybenzyl)-1,4,7-triazacyclononane) and Cd(HL2)(H2O)2 (CdL2, L2 = 1,4,7-tris(3-(4-benzoate)prop-2-yn-1-yl)-1,4,7-triazacyclononane) based on 1,4,7-triazacyclononane N-functionalized by different arylcarboxylic acids were prepared under solvothermal conditions and characterized by single crystal X-ray analysis and porosity measurements. The crystal structure of Cd2L1 reveals a cationic net with a bcs topology, and nodes are constituted by dinuclear cadmium complexes, in which each cadmium atom adopts a hexacoordinated environment involving both the carboxylate and the cyclic amine. In contrast, CdL2 displays a 2-fold interpenetrated structure with a pcu topology. In this net, the node is a mononuclear complex in which the Cd atom exhibits a seven-coordination geometry. Both materials show a high permanent porosity and good CO2 adsorption properties with a high selectivity over N2 and CH4. The adsorption capacity and selectivity for CO2 were calculated from a multisite Langmuir isotherm model and the ideal adsorbed solution theory, which gave insights into the nature of solid-gas interactions and showed the influence of interpenetration or polarity of the charged framework on their adsorption properties.
- Feuchter, Hervé,Ortiz, Guillaume,Rousselin, Yoann,Bessmertnykh-Lemeune, Alla,Brandès, Stéphane
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p. 3665 - 3676
(2017/07/12)
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- Sodium Phenoxide Mediated Hydroxymethylation of Alkynylsilanes with N-[(Trimethylsiloxy)methyl]phthalimide
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The hydroxymethylation of alkynylsilanes with formaldehyde generated in situ from N-[(trimethylsiloxy)methyl]phthalimide proceeds in the presence of a stoichiometric amount of NaOPh. The reaction occurs at room temperature by using an operationally simple one-step procedure. A variety of alkynylsilanes possessing electron-donating, electron-withdrawing, and halogen groups (including heteroaryl-substituted alkynylsilanes) provide hydroxymethylated products.
- Asano, Narumi,Sasaki, Keita,Chataigner, Isabelle,Shigeno, Masanori,Kondo, Yoshinori
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supporting information
p. 6926 - 6930
(2017/12/26)
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- Gold(I)-Initiated Cycloisomerization/Diels-Alder/Retro-Diels-Alder Cascade Strategy to Biaryls
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A unique approach to biaryls was developed on the basis of propargyl vinyl ethers and dienophiles substrates via a gold(I)-initiated cycloisomerization/Diels-Alder/retro-Diels-Alder cascade reaction. The scope and mechanism of the reaction were investigated on the basis of a series of synthetic substrates, control experiments, and DFT calculations.
- Jin, Shengfei,Niu, Yujie,Liu, Chengjun,Zhu, Lifeng,Li, Yangming,Cui, Shanshan,Xiong, Zhiling,Cheng, Maosheng,Lin, Bin,Liu, Yongxiang
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p. 9066 - 9074
(2017/09/11)
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- Enantioselective Formation of CF3-Bearing All-Carbon Quaternary Stereocenters via C-H Functionalization of Methanol: Iridium Catalyzed Allene Hydrohydroxymethylation
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Using an iridium catalyst modified by PhanePhos, CF3-allenes react with methanol to form branched products of hydrohydroxymethylation as single regioisomers with excellent levels of enantiomeric enrichment. This hydrogen autotransfer process enables catalytic enantioselective formation of acyclic CF3-bearing all-carbon quaternary stereocenters in the absence of stoichiometric metals or byproducts.
- Holmes, Michael,Nguyen, Khoa D.,Schwartz, Leyah A.,Luong, Tom,Krische, Michael J.
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supporting information
p. 8114 - 8117
(2017/06/28)
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- Construction of Condensed Polycyclic Aromatic Frameworks through Intramolecular Cycloaddition Reactions Involving Arynes Bearing an Internal Alkyne Moiety
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Facile synthetic methods for condensed polycyclic aromatic compounds via aryne intermediates are reported. The generation of arynes bearing a (3-arylpropargyl)oxy group from the corresponding o-iodoaryl triflate-type precursors efficiently afforded arene-fused oxaacenaphthene derivatives, which were formed through intramolecular [2+4] cycloaddition. Extending the method to the generation of arynes bearing a 1,3-diyne moiety led to a continuous generation of naphthalyne intermediate through the hexadehydro Diels–Alder reaction involving the aryne triple bond. This novel type of aryne-relay chemistry enabled the synthesis of a unique aminoarylated oxaacenaphthene derivative and highly ring-fused anthracene derivatives.
- Yoshida, Suguru,Shimizu, Keita,Uchida, Keisuke,Hazama, Yuki,Igawa, Kazunobu,Tomooka, Katsuhiko,Hosoya, Takamitsu
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supporting information
p. 15332 - 15335
(2017/10/18)
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- Copper-Catalyzed Enantio-, Diastereo-, and Regioselective [2,3]-Rearrangements of Iodonium Ylides
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The first highly enantioselective, diastereoselective, and regioselective [2,3]-rearrangement of iodonium ylides has been developed as a general solution to catalytic onium ylide rearrangements. In the presence of a chiral copper catalyst, substituted allylic iodides couple with α-diazoesters to generate metal-coordinated iodonium ylides, which undergo [2,3]-rearrangements with high selectivities (up to >95:5 r.r., up to >95:5 d.r., and up to 97 % ee). The enantioenriched iodoester products can be converted stereospecifically into a variety of onium ylide rearrangement products, as well as compounds that are not accessible by classical onium ylide rearrangements.
- Xu, Bin,Tambar, Uttam K.
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supporting information
p. 9868 - 9871
(2017/08/08)
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- Photoredox-catalyzed oxytrifluoromethylation of allenes: Stereoselective synthesis of 2-trifluoromethylated allyl acetates
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We have developed novel oxytrifluoromethylation of aryl-substituted allenes by photoredox catalysis. The present photocatalytic system allows direct and stereoselective synthesis of 2-CF3-allyl acetates bearing tetrasubstituted CF3-a
- Tomita, Ren,Koike, Takashi,Akita, Munetaka
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supporting information
p. 4681 - 4684
(2017/07/10)
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- Ultrafast Electron Transfers in Organometallic Supramolecular Assemblies Built with a NIR-Fluorescent Tetrabenzoporphyrine Dye and the Unsaturated Cluster Pd3(dppm)3(CO)2+
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The sodium 9,18,27,36-tetra-(4-carboxyphenylethynyl)tetrabenzoporphyrinatozinc(II) (TCPEBP) and sodium 5,10,15,20-tetra-(4-carboxyphenylethynyl)porphyrinatozinc(II) (TCPEP, for comparison purposes) salts were prepared to investigate the ionic driven host-guest assemblies made with the unsaturated redox-active cluster Pd3(dppm)3(CO)2+ ([Pd32+], dppm = Ph2PCH2PPh2 as a PF6- salt). Nonemissive dye?[Pd32+]x assemblies (x = 1-4) are formed in methanol with K1x (binding constants) values of 83 200 (TCPEBP) and 70 400 M-1 (TCPEP; average values extracted from graphical methods (Benesi-Hildebrand, Scott, and Scatchard), matching those obtained from fluorescence quenching experiments (static model)). These values are consistent with the more electron rich TCPEBP dye. This conclusion is corroborated by electrochemical data, which indicate a lower oxidation potential of the TCPEBP dye (+0.46 V) vs TCPEP (+0.70 V vs SCE) and by shorter calculated average Pd?O distances (DFT (B3LYP): 3.259 vs 3.438 ?, respectively). Using the position of the 0-0 component of the Q-bands and the electrochemical data, the excited-state driving forces for dye??[Pd32+]x → dye+??[Pd3+?][Pd32+]x-1 are estimated for TCPEBP (+1.22 V vs SCE) and TCPEP (1.08 V vs SCE). The time scale for this process occurs within the laser pulse (fwhm +??[Pd3+?][Pd32+]x-1 → dye?[Pd32+]x) occur well within 1 ps (respectively 650 and 170 fs for TCPEBP and TCPEP). Arguments are provided that the reorganization energy governs this difference.
- Luo, Peng,Karsenti, Paul-Ludovic,Brisard, Gessie,Marsan, Benoit,Harvey, Pierre D.
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supporting information
p. 816 - 826
(2016/03/30)
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- Enantioselective Carbene Cascade: An Effective Approach to Cyclopentadienes and Applications in Diels–Alder Reactions
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An asymmetric carbene cascade reaction, which proceeds through carbene/alkyne metathesis and formal (3+2) cycloaddition and converts alkynyl-tethered enol diazoacetates to chiral bicyclic cyclopentadienes, is presented; and no catalytic asymmetric version of these carbene cascade transformations has been disclosed so far. The proton signals of the cyclopropene intermediates are observed in the mechanism study, which clearly demonstrate the reaction pathways. In addition, these products are intercepted via Diels–Alder reactions to provide bridged polycyclic structures in high yields and enantioselectivities. (Figure presented.).
- Wang, Xiangbo,Zhou, Yunfei,Qiu, Lihua,Yao, Ruwei,Zheng, Yang,Zhang, Cheng,Bao, Xiaoguang,Xu, Xinfang
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supporting information
p. 1571 - 1576
(2016/10/13)
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- Ligand-Controlled Regiodivergence in the Copper-Catalyzed [2,3]- and [1,2]-Rearrangements of Iodonium Ylides
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Despite the importance of allylic ylide rearrangements for the synthesis of complex molecules, the catalyst control of [2,3]- and [1,2]-rearrangements remains an unsolved problem. We developed the first regiodivergent [2,3]- and [1,2]-rearrangements of iodonium ylides that are controlled by copper catalysts bearing different ligands. In the presence of a 2,2′-dipyridyl ligand, diazoesters and allylic iodides react via a [2,3]-rearrangement pathway. Alternatively, a phosphine ligand favors the formation of the [1,2]-rearrangement product. A series of α-iodoesters containing a broad range of functional groups were obtained in high yields, regioselectivities, and diastereoselectivities. Deuterium-labeling studies suggest distinct mechanisms for the regioselective rearrangements.
- Xu, Bin,Tambar, Uttam K.
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supporting information
p. 12073 - 12076
(2016/09/28)
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- Fluorene derivative
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The invention relates to novel fluorene derivatives, which are especially suitable for use in birefringent films with negative optical dispersion, to novel liquid crystal (LC) formulations and polymer films comprising them, and to the use of the fluorene
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Paragraph 0265-0268
(2017/01/12)
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- Catalytic Asymmetric Synthesis of Alkynyl Aziridines: Both Enantiomers of cis-Aziridines from One Enantiomer of the Catalyst
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Alkynyl aziridines can be obtained from the catalytic asymmetric aziridination (AZ reaction) of alkynyl imines with diazo compounds in high yields and high asymmetric inductions mediated by a chiral boroxinate or BOROX catalyst. In contrast to the AZ reaction with aryl- and alkyl-substituted imines, alkynyl imines react to give cis-substituted aziridines with both diazo esters and diazo acetamides. Remarkably, however, the two diazo compounds give different enantiomers of the cis-aziridine from the same enantiomer of the catalyst. Theoretical considerations of the possible transition states for the enantiogenic step reveal that the switch in enantiomers results from a switch from Si-face to Re-face addition to the imine, which in turn is related to a switch from reaction with an E-imine in the former and a Z-isomer of the imine in the latter. The imine did it: The aziridination of alkynyl imines with diazo esters and diazo acetamides gives cis-aziridines with very high enantioselectivities. The absolute configuration of the cis-aziridine is reversed for the two diazo compounds even though the same enantiomer of the catalyst is used. The alkynyl imines can isomerize under the reaction conditions and the enantiomeric switch is proposed to result from the preferential reaction of E-imine with diazo esters and Z-imines with diazo acetamides.
- Guan, Yong,L?pez-Alberca, Maria P.,Lu, Zhenjie,Zhang, Yu,Desai, Aman A.,Patwardhan, Aniruddha P.,Dai, Yijing,Vetticatt, Mathew J.,Wulff, William D.
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supporting information
p. 13894 - 13900
(2016/02/18)
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- Preparation and evaluation of novel pyrazolo[1,5-a]pyrimidine acetamides, closely related to DPA-714, as potent ligands for imaging the TSPO 18 kDa with PET
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A series of four novel analogues of DPA-714, bearing a fluoroalkynyl side chain (with a length ranging from three to six carbon atoms) in replacement of the fluoroethoxy motif, have been synthetized in six steps from commercially available methyl 4-iodobe
- Médran-Navarrete, Vincent,Damont, Annelaure,Peyronneau, Marie-Anne,Kuhnast, Bertrand,Bernards, Nicholas,Pottier, Géraldine,Marguet, Frank,Puech, Frédéric,Boisgard, Rapha?l,Dollé, Frédéric
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p. 1550 - 1556
(2014/03/21)
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- Zinc-catalyzed [4+3] cycloaddition with concomitant furan annulation: Formation of cyclohepta[b]furans
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A convenient zinc-promoted [4+3] cycloaddition of a carbonyl ene-yne with simple dienes was first achieved. This reaction provided an efficient strategy to prepare various cyclohepta[b]furan rings by cascade cycloadditions. Additionally, a multicomponent reaction of dione, alkynal, and diene was also reported, which exhibited a novel strategy for selective creations of C-O bonds and C-C bonds. Go tandem! A first zinc-catalyzed tandem [4+3] cycloaddition is presented herein. Various substituted cyclohepta[b]furans were synthesized from carbonyl ene-yne and diene in moderate to good yield. Furan rings and seven-membered rings were prepared in one single step (see scheme; TBS=tert-butyldimethyl).
- Song, Bo,Li, Lian-Hua,Song, Xian-Rong,Qiu, Yi-Feng,Zhong, Mei-Jin,Zhou, Ping-Xin,Liang, Yong-Min
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supporting information
p. 5910 - 5913
(2014/05/20)
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- Enantioselective synthesis of trans-aryl-and-heteroaryl-substituted cyclopropylboronates by copper (I)-catalyzed reactions of allylic phosphates with a diboron derivative
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A new asymmetric route for the synthesis of trans-2-aryl- and -heteroaryl-substituted cyclopropylboronates has been developed. (Z)-3-arylallylic phosphates were converted to the optically active products with high yield and diastereo- and enantioselectivity through a copper(I)-catalyzed reaction with a diboron derivative. Under mild reaction conditions, the reaction affords the arylcyclopropane products with a functional group and a heteroaromatic group in a highly enantioselective manner. When (E)-allylic phosphates were used as substrates, a ligand-controlled product switch between the trans and cis configurations was observed.
- Zhong, Chongmin,Kunii, Shun,Kosaka, Yuki,Sawamura, Masaya,Ito, Hajime
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supporting information; experimental part
p. 11440 - 11442
(2010/10/04)
-
- 5-Substituted isoquinoline derivatives
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A compound represented by the following formula (1) or a salt thereof: wherein R1 represents hydrogen atom, a halogen atom and the like; R2 represents hydrogen atom, a halogen atom, a C1-6 alkyl group and the like; and R3 represents —O—X—C(A1)(A11)—C(A2)(A2l)—N(A3l)(A3)(X represents propylene group etc., A11 and A21 represent hydrogen atom, or a C1-6 alkyl group, A31 represents a C1-6 alkyl group substituted with hydroxyl group, or hydrogen atom, and A1, A2, and A3 represent hydrogen atom, a C1-6 alkyl group and the like) and the like, which has an inhibitory activity on the phosphorylation of myosin regulatory light chain, and is useful for treatment of diseases relating to contraction of various cells and the like.
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- EP4 receptor selective agonists in the treatment of osteoporosis
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This invention is directed to EP4 receptor selective prostaglandin agonists of the Formula I, wherein R2, X, Z and Q are as defined in the specification. This invention is also directed to pharmaceutical compositions containing those compounds. This invention is also directed to methods of treating conditions which present with low bone mass, particularly osteoporosis, frailty, an osteoporotic fracture, a bone defect, childhood idiopathic bone loss, alveolar bone loss, mandibular bone loss, bone fracture, osteotomy, bone loss associated with periodontitis, or prosthetic ingrowth in a mammal comprising administering those compounds.
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- Unexpected Course of the Reaction of 1,3-Bis(dimethylamino)trimethinium Perchlorate with 3-Substituted Prop-2-ynals Leading to 1-Aryl-2,4,6-triformylbenzenes
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Reaction of 1,3-bis(dimethylamino)trimethinium perchlorate (1) with 3-substituted prop-2-ynals (4) in acetic anhydride at the presence of ZnBr2 gives upon hydrolysis 1-substituted 2,4,6-triformylbenzenes (6) in low to moderate yield. This reaction is restricted to prop-2-ynals bearing electron rich aromatic substituents at the 3-position.
- Suchy, Petr,Dvorak, Dalimil,Havelkova, Martina
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p. 119 - 129
(2007/10/03)
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- METHODS FOR PREPARING ANTIPROLIFERATIVE 5-SUBSTITUTED PYRIMIDONE COMPOUNDS
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Intermediates for preparing derivatives of 5-thia- and5-selenopyrimidinone which are useful as inhibitors of the enzymes glydnamide ribonucleotide formyl transferase (GARFT) and amino imidazole carboxamide ribonucleotide formyl transferase (AICARFT). The present invention is also directed to methods of preparing these intermediates
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- Antiproliferative substituted 5-thiapyrimidinone and 5-selenopyrimidinone compounds
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The present invention is directed to derivatives of 5-thia- and 5-selenopyrimidinone, which are useful as inhibitors of the enzymes glycinamide ribonucleotide formyl transferase (GARFT) and amino imidazole carboxamide ribonucleotide formyl transferase AICARFT), pharmaceutical compositions containing these derivatives, and methods of using these derivatives. The present invention is also directed to intermediates useful for preparing these derivatives and methods of preparing these intermediates.
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- Protein structure-based design, synthesis, and biological evaluation of 5-thia-2,6-diamino-4(3H)-oxopyrimidines: Potent inhibitors of glycinamide ribonucleotide transformylase with potent cell growth inhibition
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The design, synthesis, biochemical, and biological evaluation of a novel series of 5-thia-2,6-diamino-4(3H)-oxopyrimidine inhibitors of glycinamide ribonucleotide transformylase (GART) are described. The compounds were designed using the X-ray crystal structure of human GART. The monocyclic 5- thiapyrimidinones were synthesized by coupling an alkyl thiol with 5-bromo- 2,6-diamino-4(3H)-pyrimidinone, 20. The bicyclic compounds were prepared in both racemic and diastereomerically pure forms using two distinct synthetic routes. The compounds were found to have human GART K(i)s ranging from 30 μM to 2 nM. The compounds inhibited the growth of both L1210 and CCRF-CEM cells in culture with potencies down to the low nanomolar range and were found to be selective for the de hove purine biosynthesis pathway. The most potent inhibitors had 2,5-disubstituted thiophene rings attached to the glutamate moiety. Placement of a methyl substituent at the 4-position of the thiophene ring to give compounds 10, 18, and 19 resulted in inhibitors with significantly decreased mFBP affinity.
- Varney, Michael D.,Palmer, Cindy L.,Romines III, William H.,Boritzki, Theodore,Margosiak, Stephen A.,Almassy, Robert,Janson, Cheryl A.,Bartlett, Charlotte,Howland, Eleanor J.,Ferre, Rosanne
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p. 2502 - 2524
(2007/10/03)
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- Synthesis and biological evaluation of a new series of dihydrofolate reductase inhibitors based on the 4-(2,6-diamino-5-pyrimidinyl)alkyl-L-glutamic acid structure
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A novel series of dihydrofolate reductase inhibitors was uncovered during an expansion of the SAR of 5,10-dideazatetrahydrofolic acid, and their biological activity was evaluated. These new analogs do not possess an oxygen at the 4 position and contain a
- Gossett, Lynn S.,Habeck, Lillian L.,Gates, Susan B.,Andis, Sherri L.,Worzalla, John F.,Schultz, Richard M.,Mendelsohn, Laurane G.,Kohler, William,Ratnam, Manohar,Grindey, Gerald B.,Shih, Chuan
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p. 473 - 476
(2007/10/03)
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- PYRIMIDINYL-GLUTAMIC ACID DERIVATIVES
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The present invention provides novel pyrimidinyl-glutamic acid derivatives and intermediates thereto. Further provided are methods for inhibiting dihydrofolate reductase in mammals and for treating susceptible neoplasms in mammals, particularly humans.
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- Cyclopropanecarboxylic acid alkynyl esters, processes for producing them, and their use as pesticides
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Cyclopropanecarboxylic acid alkynyl esters of the formula I STR1 wherein R1 is unsubstituted or substituted phenyl or thienyl, R2 is hydrogen, alkyl having 1-6 C atoms, alkenyl having 2-6 C atoms, or phenyl or naphthyl which is unsubstituted or substituted by an alkyl or alkoxy group having 1-2 C atoms or by a halogen atom, and R3 is hydrogen, alkyl having 1-6 C atoms or alkenyl having 2-6 C atoms, are suitable for combating various plant and animal pests, particularly insects, and members of the order Acarina. They can be obtained by reaction of corresponding alkynols with cyclopropanecarboxylic acid or with a reactive functional derivative thereof.
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