- SuFEx on the Surface: A Flexible Platform for Postpolymerization Modification of Polymer Brushes
-
Polymer brushes present a unique architecture for tailoring surface functionalities due to their distinctive physicochemical properties. However, the polymerization chemistries used to grow brushes place limitations on the monomers that can be grown direc
- Yatvin, Jeremy,Brooks, Karson,Locklin, Jason
-
-
Read Online
- Meldrum's acid-derived thione dienophile in a convergent and stereoselective synthesis of a tetracyclic quassinoid intermediate
-
An advanced intermediate toward anti-cancer quassinoids has been synthesized using a quadruple diene-transmissive [4+2]-cycloaddition strategy. High convergence is achieved thanks to a regio- and stereoselective hetero-Diels-Alder reaction using a thione. The relative stereochemistry of the final Diels-Alder adduct was controlled by tethered substituents introduced via a highly syn- and γ-selective vinylogous Mukaiyama aldol.
- Perreault, Stephane,Spino, Claude
-
-
Read Online
- Synthesis and biological evaluation of novel non-racemic indole-containing allocolchicinoids
-
Two novel indole-containing allocolchicinoids were prepared from naturally occurring colchicine exploiting the Curtius rearrangement and tandem Sonogashira coupling/Pd-catalyzed cyclization as the key transformations. Their cytotoxic properties, apoptosis-inducing activity, tubulin assembly inhibition and short-time cytotoxic effects were investigated. Compound 7 demonstrated the most pronounced anti-cancer activity: IC50 1 nM, cell cycle arrest in the G2/M phase, 25% apoptosis induction, as well as lower destructive short-time effects on HT-29 cell line in comparison with colchicine. Docking studies for prepared indole-derived allocolchicine analogues were carried out.
- Shchegravina, Ekaterina S.,Maleev, Alexander A.,Ignatov, Stanislav K.,Gracheva, Iuliia A.,Stein, Andreas,Schmalz, Hans-Günther,Gavryushin, Andrey E.,Zubareva, Anastasiya A.,Svirshchevskaya, Elena V.,Fedorov, Alexey Yu.
-
-
Read Online
- A highly efficient and selective synthesis of lissoclinolide featuring hydrogen transfer hydrozirconation, trans-selective Pd-catalyzed cross coupling of alkenylzirconiums with 1,1-dibromoalkenes and Ag-catalyzed lactonization providing (Z)-γ-alkylidenebu
-
An antibiotic lissoclinolide has been synthesized from propargyl alcohol in 9 steps and in 32% overall yield via (i) hydrogen transfer hydrozirconation of TBS-protected propargyl alcohol with i-BuZrCp2Cl, (ii) Pd-catalyzed trans-selective cross
- Xu, Caiding,Negishi, Ei-ichi
-
-
Read Online
- Reverse Brook rearrangement of 2-alkynyl trialkylsilyl ether. Synthesis of optically active (1-hydroxy-2-alkynyl)trialkylsilane
-
A new method for the synthesis of optically active α-hydroxyalkynylsilane 3 is described. The key step of the conversion to 3 was the use of the reverse Brook rearrangement of the 2-alkynyl silyl ether 2. (C) 2000 Elsevier Science Ltd.
- Sakaguchi,Fujita,Suzuki,Higashino,Ohfune
-
-
Read Online
- Synthesis of α-substituted α,β-unsaturated acylsilanes
-
α-Deprotonation of tert-butyldimethylsilyloxy allene is followed by silyl migration from oxygen to carbon. The resulting C-nucleophile adds to aldehydes to generate α,β-unsaturated acylsilanes.
- Tius, Marcus A.,Hu, Huaping
-
-
Read Online
- Stereoselective formation of 1,4-dialkoxy-1,3-dienes from propargyl ethers and molybdenum carbene complexes
-
Under mild conditions 1,4-dialkoxy-1,3-butadienes can be smoothly prepared with a high level of stereoselectivity by thermolysis of molybdenum carbene complexes in the presence of propargyl ethers.
- Harvey,Neil
-
-
Read Online
- The Total Synthesis of the Clerodane Diterpene Insect Antifeedant Ajugarin I
-
The first total synthesis of the polyoxygenated diterpene insect antifeedant ajugarin I (1) has been achieved by a route which involves a new method for the construction of 3-substituted-Δ2-butenolides.
- Ley, Steven V.,Simpkins, Nigel S.,Whittle, Alan J.
-
-
Read Online
- COMPOUNDS AND METHODS OF USE
-
Disclosed are heterocyclic compounds or their pharmaceutically acceptable salts with ferroptosis-inducing activity, Those compounds or their pharmaceutically acceptable salts can be used to treat cancer.
- -
-
Page/Page column 220-221
(2022/03/09)
-
- Mechanistic Details of Asymmetric Bromocyclization with BINAP Monoxide: Identification of Chiral Proton-Bridged Bisphosphine Oxide Complex and Its Application to Parallel Kinetic Resolution
-
The mechanism of our previously reported catalytic asymmetric bromocyclization reactions using 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) monoxide was examined in detail by the means of control experiments, NMR studies, X-ray structure analysis, and CryoSpray electrospray ionization mass spectrometry (ESI-MS) analysis. The chiral BINAP monoxide was transformed to a key catalyst precursor, proton-bridged bisphosphine oxide complex (POHOP·Br), in the presence of N-bromosuccinimide (NBS) and contaminating water. The thus-formed POHOP further reacts with NBS to afford BINAP dioxide and molecular bromine (Br2) simultaneously in equimolar amounts. While the resulting Br2 is activated by NBS to form a more reactive brominating reagent (Br2─NBS), BINAP dioxide serves as a bifunctional catalyst, acting as both a Lewis base that reacts with Br2─NBS to form a chiral brominating agent (P═O+─Br) and also as a Br?nsted base for the activation of the substrate. By taking advantage of this novel concerted Lewis/Br?nsted base catalysis by BINAP dioxide, we achieved the first regio- and chemodivergent parallel kinetic resolutions (PKRs) of racemic unsymmetrical bisallylic amides via bromocyclization.
- Hamashima, Yoshitaka,Hirokawa, Ryo,Hisanaga, Tatsunari,Ichikawa, Mamoru,Kawato, Yuji,Nagao, Yoshihiro,Takita, Ryo,Watanabe, Kohei,Yamashita, Kenji
-
supporting information
p. 3913 - 3924
(2022/03/15)
-
- PROBE FOR DETECTING CARBAPENEM-RESISTANT BACTERIA AND USE THEREOF
-
The present disclosure relates to a compound represented by Chemical Formula 1, a probe for detecting antibiotic-resistant bacteria, which includes the compound, a composition containing the compound, a kit including the compound and a method for detectin
- -
-
Paragraph 0085; 0096-0098
(2021/09/10)
-
- 3,6-DIAMINO-PYRIDAZIN-3-YL DERIVATIVES, PHARMACEUTICAL COMPOSITIONS CONTAINING THEM AND THEIR USES AS PRO-APOPTOTIC AGENTS
-
Compounds of formula (I) wherein Het1, Het2, R1, R2 and R3 are as defined in the description. Medicaments.
- -
-
Page/Page column 130
(2021/02/05)
-
- Regio-divergent nickel catalysis: intramolecular [4+2] and [2+2] cycloaddition reactions between vinylallenes and alkynes
-
Vinylallenes have been recognized as versatile C2 and C4 components for nickel-catalyzed intramolecular [4+2] and [2+2] cycloadditions. The former reaction was promoted by a Ni(0) complex (up to quantitative yield), and a Ni(ii) salt was a key species for
- Arai, Shigeru,Inagaki, Saki,Nakajima, Masaya,Nishida, Atsushi
-
supporting information
p. 11268 - 11271
(2021/11/03)
-
- DERIVATIVES OF THAILANSTATIN A, METHODS OF TREATMENT AND METHODS OF SYNTHESIS THEREOF
-
In one aspect, the present disclosure provides analogs of thailanstatin of the formula wherein the variables are as defined herein. In another aspect, the present disclosure also provides methods of preparing the compounds disclosed herein. In another aspect, the present disclosure also provides pharmaceutical compositions and methods of use of the compounds disclosed herein.
- -
-
Paragraph 0311
(2020/02/10)
-
- Enantioselective Addition of Alkynyl Esters and Ethers to Aldehydes Catalyzed by a Cyclopropyl Amino Alcohol Based Zinc Catalyst
-
A novel and highly enantioselective synthesis of hydroxyalkynyl esters and ethers through the asymmetric addition of alkynyl esters or ethers to aldehydes promoted by a cyclopropyl amino alcohol based zinc catalyst has been developed. The method afforded a library of new enantioenriched hydroxyalkynol esters and ethers (up to 93percent yield; 95percent ee), and it was compatible with a broad range of functional groups. Moreover, it could be used in the synthesis of carbon-chain-elongated enantioenriched hydroxyalkynol esters and (2 R,5 R)-musclide-A1, a cardiotonic potentiating principle from musk.
- Bian, Qinghua,Li, Fengqi,Li, Shuoning,Ma, Sijie,Walsh, Patrick J.,Wang, Lifeng,Wang, Min,Zhong, Jiangchun,Zhou, Yun
-
supporting information
p. 60 - 64
(2019/12/30)
-
- Diboration of 3-substituted propargylic alcohols using a bimetallic catalyst system: access to (Z)-allyl, vinyldiboronates
-
The diboration of substituted propargylic alcohols has been achieved using a bimetallic Pd/Cu catalyst system. Thein situformation of a pentrafluoroboronic acid intermediate sufficiently activates the C-O bond towards dual catalysis affording (Z)-allyl, vinyldiboronates stereoselectively.
- Peck, Cheryl L.,Nekvinda, Jan,Santos, Webster L.
-
supporting information
p. 10313 - 10316
(2020/09/16)
-
- Synthesis of 2-Amino-1,3-dienes from Propargyl Carbonates via Palladium-Catalyzed Carbon-Nitrogen Bond Formation
-
A catalytic method to synthesize 1,3,-dienes from propargylic precursors is reported. This palladium-catalyzed carbon-nitrogen bond-forming reaction furnishes 2-amino-1,3-dienes in excellent yields (up to 98%) and shows a broad tolerance to functional group diversity. The reaction has been demonstrated for over 30 amine substrates, including anilines and indoles, and proceeds under mild neutral conditions. The resulting 1,3-dienes are of great synthetic interest because of their further reaction potential.
- O'Broin, Calvin Q.,Guiry, Patrick J.
-
supporting information
p. 879 - 883
(2020/02/04)
-
- IRAK DEGRADERS AND USES THEREOF
-
The present invention provides compounds, compositions thereof, and methods of using the same.
- -
-
Paragraph 00962; 005077-005078
(2020/06/19)
-
- SMARCA DEGRADERS AND USES THEREOF
-
The present invention provides compounds, pharmaceutically acceptable compositions thereof, and methods of using the same for the modulation of one or more SWI/SNF-related matrix associated actin dependent regulator of chromatin subfamily A (SMARCA) and/or polybromo-1 (PB-1) protein via ubiqitination and/or degradation by compounds. The compounds are bifunctional molecules that link a cereblon-binding moiety to a ligand that binds SMARCA and/or PB1 proteins.
- -
-
Paragraph 00768; 00769
(2020/12/30)
-
- TERT-BUTYL (S)-2-(4-(PHENYL)-6H-THIENO[3,2-F][1,2,4]TRIAZOLO[4,3-A] [1,4]DIAZEPIN-6-YL) ACETATE DERIVATIVES AND RELATED COMPOUNDS AS BROMODOMAIN BRD4 INHIBITORS FOR TREATING CANCER
-
The present disclosure relates to te rt-butyl (S)-2-(4-(phenyl)-6H-thieno[3,2-f][l,2,4]triazolo[4,3-a] [l,4]diazepin-6-yl) acetate derivatives and related compounds as bromodomain BRD4 inhibitors for treating cancer. Exemplary compounds are e.g. tert-butyl (S)-2-(4-(4-(3-aminoprop-l-yn-l-yl)phenyl)-2,3,9-trimethyl-6H-thieno[3,2-f][l,2,4]triazolo[4,3-a][l,4]diazepin-6-yl)acetate (example 1, compound la), tert-butyl(S,E)-2-(4-(4-(3-aminoprop-l-en-l-yl)phenyl)-2,3,9-trimethyl-6H-thieno[3,2-f][l,2,4]triazolo[4,3-a][l,4]diazepin-6-yl)acetate (example 6, compound 6a) or tert-butyl(S)-2-(4-(4-(3-(hydroxyamino)prop-l-yn-l-yl)phenyl)-2,3,9-trimethyl-6H-thieno[3,2-f][l,2,4]triazolo[4,3-a] [l,4]diazepin-6-yl)acetate (example 8, compound 8a).Results of biological assays, such as e.g. BRD4 BD1 and BD2 binding (table 2), cell proliferation assays (table 6) and inhibition of MYC expression in MV-4-11 cells (table 7) are disclosed.
- -
-
Paragraph 0326
(2020/05/06)
-
- Concise Total Synthesis of (?)-Vermiculine through a Rhodium-Catalyzed C2-Symmetric Dimerization Strategy
-
A short and efficient synthesis of the C2-symmetric antibiotic (?)-vermiculine by utilizing an enantioselective catalytic one-step dimerization methodology as key-step to construct the core structure is reported. The late-stage modifications feature a double metathesis homologation followed by a double Wacker-type oxidation. These key-steps allowed the synthesis of vermiculine in only seven steps, starting from commercially available building blocks.
- Steib, Philip,Breit, Bernhard
-
supporting information
p. 3532 - 3535
(2019/02/19)
-
- SUBSTITUTED 3-PHENYLQUINAZOLIN-4(3H)-ONES AND USES THEREOF
-
The present invention covers substituted 3-Phenylquinazolin-4(3H)-one compounds of general formula (I) as described and defined herein, methods of preparing said compounds, intermediate compounds useful for preparing said compounds, pharmaceutical compositions and combinations comprising said compounds, and the use of said compounds for manufacturing pharmaceutical compositions for the treatment or prophylaxis of diseases, in particular for the treatment and/or prophylaxis of various inflammatory and fibrotic diseases of the respiratory tract and of the lungs as well as lung cancer, as a sole agent or in combination with other active ingredients.
- -
-
Page/Page column 98
(2019/04/26)
-
- Highly Chemo- and Stereoselective Catalyst-Controlled Allylic C?H Insertion and Cyclopropanation Using Donor/Donor Carbenes
-
The highly chemo-, enantio-, and diastereoselective catalyst-controlled intramolecular allylic C?H insertion and cyclopropanation of donor/donor carbenes are reported. The RuII/Pybox complex selectively catalyzed the intramolecular allylic C?H
- Zhu, Dong,Chen, Lianfen,Zhang, He,Ma, Zhiqiang,Jiang, Huanfeng,Zhu, Shifa
-
supporting information
p. 12405 - 12409
(2018/09/18)
-
- Synthesis of multi-substituted dihydrofurans via palladium-catalysed coupling between 2,3-alkadienols and pronucleophiles
-
Multi-substituted dihydrofurans were obtained from a palladium-catalysed coupling reaction between 2,3-alkadienols and ketones bearing an electron-withdrawing group at the α-position. Methanol as a solvent was essential for the initial dehydrative substitution to suppress the competitive hydroalkylation of the diene moiety. The substitution would be followed by intramolecular hydroalkoxylation under the same catalysis.
- Tsukamoto, Hirokazu,Ito, Kazuya,Doi, Takayuki
-
supporting information
p. 5102 - 5105
(2018/05/26)
-
- Studies towards the total synthesis of cruentaren A and B: Stereoselective synthesis of fragments C1-C11, C12-C22 and C23-C28
-
A convergent and stereoselective approach for the synthesis of C1-C11, C12-C22, and C23-C28 fragments of cytotoxic natural products cruentaren A and B are accomplished. Highlights of the strategy include a Sharpless epoxidation followed by a regioselective opening of epoxide to generate anti and syn-stereochemistry at C9-C10 and C15-C16, an Alder-Rickert reaction between a 1,5-dimethoxy-1,4-cyclohexadiene and dienophile to construct the aromatic ring, and a lithium-mediated aldol reaction to install the C17-C18 anti-stereochemistry. The synthesis of C1-C11 and C12-C22 fragments proceed with a longest linear sequence of 10 and 17 steps from commercially available 2-butyne-1,4-diol and cis-2-butene-1,4-diol respectively.
- Ganganna, Bogonda,Srihari, Pabbaraja,Yadav, Jhillu Singh
-
supporting information
p. 2685 - 2689
(2017/06/23)
-
- Total Synthesis of (-)-Marinisporolide C
-
The first total synthesis of (-)-marinisporolide C is described, which establishes unequivocally the relative and absolute configuration of this oxopolyene macrolide. Key features of this synthesis include a series of highly stereoselective aldol reactions followed by directed reductions to build the polyol domain, a Stille cross-coupling reaction to assemble the polyene, and an intramolecular Horner-Wadsworth-Emmons olefination to forge the macrocyclic ring. Despite the initial approach to marinisporolide A using a Yamaguchi macrolactonization reaction that was unsuccessful due to steric hindrance of the oxygen at the C33 position, we were able to prepare a known derivative of marinisporolide A and consequently confirm its stereochemical assignment.
- Dias, Luiz C.,De Lucca, Emilio C.
-
p. 3019 - 3045
(2017/03/23)
-
- Synthesis of Functionalized [3], [4], [5] and [6]Dendralenes through Palladium-Catalyzed Cross-Couplings of Substituted Allenoates
-
A mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patter
- Lippincott, Daniel J.,Linstadt, Roscoe T. H.,Maser, Michael R.,Lipshutz, Bruce H.
-
supporting information
p. 847 - 850
(2017/01/14)
-
- Ethylene Glycol Assisted Intermolecular Pauson-Khand Reaction
-
The use of ethylene glycol as additive in the N -oxide-promoted intermolecular Pauson-Khand reaction (PKR) has been studied. The addition of 15% ethylene glycol to the reaction mixture consistently increased (from 20% up to 2-4-fold) the reaction yields.
- Cabré, Albert,Verdaguer, Xavier,Riera, Antoni
-
supporting information
p. 3945 - 3951
(2017/08/29)
-
- Asymmetric total synthesis and revision of absolute configurations of azaphilone derivative felinone A
-
The first total synthesis of the azaphilone derivative, felinone A, was accomplished. The absolute configuration of natural felinone A was revised to be 3S, 6S, and 7R.
- Abe, Hideki,Tango, Haruhito,Kobayashi, Toyoharu,Ito, Hisanaka
-
supporting information
p. 4296 - 4298
(2017/10/12)
-
- Ratiometric electrochemical detection of hydrogen peroxide and glucose
-
Hydrogen peroxide (H2O2) detection is of high importance as it is a versatile (bio)marker whose detection can indicate the presence of explosives, enzyme activity and cell signalling pathways. Herein, we demonstrate the rapid and accurate ratiometric electrochemical detection of H2O2 using disposable screen-printed electrodes through a reaction-based indicator assay. Ferrocene derivatives equipped with self-immolative linkers and boronic acid ester moieties were synthesised and tested, and, through a thorough assay optimisation, the optimum probe showed good stability, sensitivity and selectivity towards H2O2. The optimised conditions were then applied to the indirect detection of glucose via an enzymatic assay, capable of distinguishing 10 μM from the background within minutes.
- Goggins, Sean,Apsey, Ellen A.,Mahon, Mary F.,Frost, Christopher G.
-
supporting information
p. 2459 - 2466
(2017/03/20)
-
- Total Synthesis of Thailanstatin A
-
The total synthesis of the spliceosome inhibitor thailanstatin A has been achieved in a longest linear sequence of nine steps from readily available starting materials. A key feature of the developed synthetic strategy is the implementation of a unique, biomimetic asymmetric intramolecular oxa-Michael reaction/hydrogenation sequence that allows diastereodivergent access to highly functionalized tetrahydropyrans, which can be used for the synthesis of designed analogues of this bioactive molecule.
- Nicolaou,Rhoades, Derek,Lamani, Manjunath,Pattanayak, Manas R.,Kumar, S. Mothish
-
supporting information
p. 7532 - 7535
(2016/07/06)
-
- Synthesis of the Bioherbicidal Fungus Metabolite Macrocidin A
-
The second total synthesis of macrocidin A afforded the bioherbicidal fungal metabolite in 16 steps starting from doubly protected l-tyrosine. The 3-octanoyl side chain with the α-methyl group and an ω-bromo epoxide already in place was attached to the te
- Haase, Robert G.,Schobert, Rainer
-
supporting information
p. 6352 - 6355
(2016/12/23)
-
- Synthesis of Nonracemic Pyrrolo-allocolchicinoids Exhibiting Potent Cytotoxic Activity
-
An efficient eight-step semisynthetic approach towards nonracemic pyrrolo-allocolchicinoids starting from natural colchicine was developed by exploiting Pd-catalyzed domino Sonogashira coupling/5-endo-dig cyclization of a 2-iodo-trifluoroacetanilide intermediate to build up the heterocyclic ring system. The N-Me substitution of the pyrrole ring enhanced the antitumor activity of the prepared molecules by 2–3 orders of magnitude. Among the active compounds, the N-methylated colchicinoid exhibited powerful cytotoxic and antiproliferative properties at concentrations 1 nm.
- Shchegravina, Ekaterina S.,Knyazev, Dmitry I.,Beletskaya, Irina P.,Svirshchevskaya, Elena V.,Schmalz, Hans-Günther,Fedorov, Alexey Yu.
-
supporting information
p. 5620 - 5623
(2016/12/14)
-
- Pyrimidine or pyridine pyridine ketone compound and its preparation method and application (by machine translation)
-
The invention discloses a kind of type I of the pyrimidine or pyridine pyridine ketone compound and its preparation and application, which belongs to the technical field of pharmaceutical preparation. The compounds have high-efficient and selectively inhibit the cell cycle dependent kinases (Cdks) CDK4 and CDK6 active, and then by inhibiting CDK4/CDK6 prevent tumor cell division. Therefore, the compounds of this invention can be used for CDK4 and CDK6 the involved in cell cycle control disorders result in various diseases, especially suitable for the treatment of malignant tumors. (by machine translation)
- -
-
Paragraph 0225
(2016/10/09)
-
- The Importance of Being Me: Magic Methyls, Methyltransferase Inhibitors, and the Discovery of Tazemetostat
-
Posttranslational methylation of histones plays a critical role in gene regulation. Misregulation of histone methylation can lead to oncogenic transformation. Enhancer of Zeste homologue 2 (EZH2) methylates histone 3 at lysine 27 (H3K27) and abnormal methylation of this site is found in many cancers. Tazemetostat, an EHZ2 inhibitor in clinical development, has shown activity in both preclinical models of cancer as well as in patients with lymphoma or INI1-deficient solid tumors. Herein we report the structure-activity relationships from identification of an initial hit in a high-throughput screen through selection of tazemetostat for clinical development. The importance of several methyl groups to the potency of the inhibitors is highlighted as well as the importance of balancing pharmacokinetic properties with potency.
- Kuntz, Kevin W.,Campbell, John E.,Keilhack, Heike,Pollock, Roy M.,Knutson, Sarah K.,Porter-Scott, Margaret,Richon, Victoria M.,Sneeringer, Chris J.,Wigle, Tim J.,Allain, Christina J.,Majer, Christina R.,Moyer, Mikel P.,Copeland, Robert A.,Chesworth, Richard
-
supporting information
p. 1556 - 1564
(2016/03/05)
-
- Rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes employing the self-assembling 6-DPPon system
-
Abstract A rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes is reported. Using a RhI/6-DPPon catalyst system, one can obtain β,γ-unsaturated aldehydes in high regio- and chemoselectivity. The Z-configured product is formed with up to >95% selectivity when unsymmetrically 1,1-disubstituted allenes are submitted to the reaction conditions. This is the first time that these interesting building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products. β,γ-Unsaturated aldehydes are obtained by a rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes. For unsymmetrically 1,1-disubstituted allenes the Z-configured product is formed in up to about 95% selectivity. This is the first time that these building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products.
- K?pfer, Alexander,Breit, Bernhard
-
supporting information
p. 6913 - 6917
(2015/06/08)
-
- Total Synthesis of the Oxopolyene Macrolide (-)-Marinisporolide C
-
The first total synthesis of (-)-marinisporolide C was performed in 25 steps (longest linear sequence) and an overall yield of 1%. Due to the high degree of convergence and robustness, the C9-C35 fragment that corresponds to the polyol portion was obtaine
- Dias, Luiz C.,De Lucca, Emílio C.
-
supporting information
p. 6278 - 6281
(2016/01/09)
-
- PYRAZOLO[1,5-a]PYRIMIDINE DERIVATIVES AS KINASE JAK-2 INHIBITORS
-
A compound of the general formula (I), useful for treating myeloproliferative, cancer,or inflammatory diseases, wherein Q represents a six-membered heteroaromatic ring containing 2 N atoms and R1 is hydrogen atom,or Q represents a five-membered heteroaromatic ring containing 1 or 2 heteroatoms selected from the group consisting of N and S,one substituent R1 is attached at C or N atom of said Q ringand R1 is selected from the group consisting of C1-C4-alkyl and C3-C4-cycloalkyl;R2 represents-NR7aR7bor-CH2-NR8aR8b;R3 represents C1-C4-alkyl;R4 represents phenylora 5-or 6-membered heteroarylcontaining 1 or 2 heteroatoms selected from the group consisting of N and S, and R4 is unsubstituted or substituted with 1 or 2 substituents selected from the group consisting of halogen, trifluoromethyl,hydroxyl and C1-C4-alkoxyl;R5 and R6 independently represent hydrogenatom or C1-C4-alkyl,and at least one of R5 and R6 represents hydrogen atom;and other substituents are as defined in the specification; and pharmaceutically acceptable salts thereof.
- -
-
Page/Page column 41
(2015/09/22)
-
- Total synthesis of the proposed structure of a polyketide from Phialomyces macrosporus
-
Total synthesis of the proposed structure of a polyketide isolated from Phialomyces macrosporus is described. The synthesis involved chemoselective epoxidation, regioselective epoxide ring opening, chemo- and diastereoselective dihydroxylation, and vinylation of lactone accompanied by the formation of a furan ring. This journal is
- Abe, Hideki,Itaya, Satoko,Sasaki, Kei,Kobayashi, Toyoharu,Ito, Hisanaka
-
supporting information
p. 3586 - 3589
(2015/03/30)
-
- Silicon-tethered strategy for copper(I)-catalyzed stereo- and regioselective alkylboration of alkynes
-
Stereoselective silicon-tethered alkylboration of alkynes in the presence of a copper(I) catalyst and a diboron reagent provided the corresponding cyclic alkenylboronates in high yields (up to 99% yield) with excellent regio- and syn-selectivities (E/Z =
- Kubota, Koji,Iwamoto, Hiroaki,Yamamoto, Eiji,Ito, Hajime
-
supporting information
p. 620 - 623
(2015/03/04)
-
- METABOTROPIC GLUTAMATE RECEPTOR NEGATIVE ALLOSTERIC MODULATORS (NAMS) AND USES THEREOF
-
Provided herein are small molecule active metabotropic glutamate subtype-2 and -3 receptor negative allosteric modulators (NAMs), compositions comprising the compounds, and methods of using the compounds and compositions.
- -
-
Paragraph 00658
(2016/01/01)
-
- Gold(I)-catalyzed intramolecular cycloisomerization of propargylic esters with furan rings
-
A gold-catalyzed intramolecular cycloisomerization of a-yne-furans 1 is described in this contribution. A variety of cyclic α,β-unsaturated aldehyde or ketone derivatives and nitrogen-containing tricyclic adducts were obtained selectively in moderate to excellent yields under mild conditions by varying the substituents on the standard substrates.
- Yang, Jin-Ming,Tang, Xiang-Ying,Shi, Min
-
supporting information
p. 4534 - 4540
(2015/03/18)
-
- Scope and Mechanistic Limitations of a Sonogashira Coupling Reaction on an Imidazole Backbone
-
A Sonogashira coupling reaction method to join terminal alkynes to the imidazole backbone was developed and investigated. The method exhibits good functional group tolerance and provides target 4-alkynylated imidazoles in 70-93% yield. The alkyne reagents were characterized by means of DFT calculations, from which electrostatic potential surfaces (EPS) were produced. A clear correlation between the EPS of the triple bond and the success of the coupling reaction was revealed. If the EPS is in range -94 to -105 kJmol-1 the coupling is successful. An unsuccessful class of reagents (alkynols) was made compatible by means of an auxiliary group (tert-butyldimethylsilyl). EPSs of these modified reagents then resembled those of the model and these auxiliary-assisted reagents then coupled successfully in excellent yields.
- Sandtorv, Alexander H.,Bj?rsvik, Hans-René
-
p. 4658 - 4666
(2015/08/03)
-
- Total synthesis of (+)-rubriflordilactone A
-
Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium- or cobalt-catalyzed cyclizations to form the CDE rings, and converge on a late-stage synthetic intermediate. These key processes are set up through the convergent coupling of a common diyne component with appropriate AB-ring aldehydes, a strategy that sets the stage for the synthetic exploration of other members of this family of natural products. Two in one: Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium- or cobalt-catalyzed cyclizations to converge on a late-stage synthetic intermediate. These key processes are set up through the coupling of a common diyne component with appropriate AB-ring aldehydes, a strategy that enables a broad exploration of this family of natural products, as well as synthetic analogues.
- Goh, Shermin S.,Chaubet, Guilhem,Gockel, Birgit,Cordonnier, Marie-Caroline A.,Baars, Hannah,Phillips, Andrew W.,Anderson, Edward A.
-
supporting information
p. 12618 - 12621
(2015/10/28)
-
- Preparation of nano silica supported sodium hydrogen sulfate: As an efficient catalyst for the trimethyl, triethyl and t-butyldimethyl silylations of aliphatic and aromatic alcohols in solution and under solvent-free conditions
-
Nano silica supported sodium hydrogen sulfate has been prepared by mixing NaHSO4 with activated Nano silicagel. We wish to report a new method for the synthesis of trimethyl (TMS), triethyl (TES) and t-butyldimethyl silyl (TBS) ethers from benzylic, allylic, propargylic alcohols, phenols, naphtholes and some of phenolic drugs in the solution and under solvent-free conditions.
- Abri, Abdolreza,Ranjdar, Somayeh
-
p. 929 - 934
(2014/10/16)
-
- Facile synthesis of halogenated spiroketals via a tandem iodocyclization
-
A strategy for the synthesis of spiroketal compounds through a tandem iodocyclization of 1-(2-ethynylphenyl)-4-hydroxybut-2-yn-1-one derivatives is presented. This reaction could proceed under very mild conditions in a short time and avoid the use of expensive and toxic metal catalysts. Moreover, the resulting halides can be further exploited by subsequent palladium-catalyzed coupling reactions, which act as the important intermediates for building other valuable compounds.
- Wang, Jia,Zhu, Hai-Tao,Li, Ying-Xiu,Wang, Li-Jing,Qiu, Yi-Feng,Qiu, Zi-Hang,Zhong, Mei-Jin,Liu, Xue-Yuan,Liang, Yong-Min
-
supporting information
p. 2236 - 2239
(2014/05/06)
-
- Non-Pd transition metal-catalyzed hydrostannations: Bu3SnF/PMHS as a tin hydride source
-
Molybdenum, cobalt, nickel, ruthenium, and rhodium catalyzed alkyne hydrostannations using in situ generated Bu3SnH were studied. In most cases, Bu3SnF+polymethylhydrosiloxane (PMHS) performed well as the in situ source of Bu3/
- Maleczka Jr., Robert E.,Ghosh, Banibrata,Gallagher, William P.,Baker, Aaron J.,Muchnij, Jill A.,Szymanski, Amy L.
-
p. 4000 - 4008
(2013/06/27)
-
- PYRIMIDINE PDE10 INHIBITORS
-
The present invention is directed to pyrimidine compounds which are useful as therapeutic agents for the treatment of central nervous system disorders associated with phosphodiesterase 10 (PDE10). The present invention also relates to the use of such compounds for treating neurological and psychiatric disorders, such as schizophrenia, psychosis or Huntington's disease, and those associated with striatal hypofunction or basal ganglia dysfunction.
- -
-
Page/Page column 49
(2013/03/26)
-
- Total syntheses of proposed (±)-trichodermatides B and C
-
Total syntheses of putative (±)-trichodermatides B and C are described. These efficient syntheses feature the oxa-[3+3] annulation strategy, leading to B and C along with their respective C2-epimers. However, these synthetic samples are spectroscopically
- Li, Qian,Xu, Yan-Shuang,Ellis, Gregory A.,Bugni, Timothy S.,Tang, Yu,Hsung, Richard P.
-
p. 5567 - 5572
(2013/09/23)
-
- Search for highly efficient, stereoselective, and practical synthesis of complex organic compounds of medicinal importance as exemplified by the synthesis of the C21-C37 fragment of amphotericinb
-
Highly stereoselective: A highly efficient, stereoselective and practical synthesis of the C21-C37 fragment of amphotericinB was realized in 25 % overall yield in eight longest linear steps from commercially available ethyl (S)-3-hydroxybutyrate by using Fráter-Seebach alkylation, Brown crotylboration, Negishi coupling, Heck reaction, and Horner-Wadsworth-Emmons (HWE) olefination as key steps (see diagram). Copyright
- Wang, Guangwei,Xu, Shiqing,Hu, Qian,Zeng, Fanxing,Negishi, Ei-Ichi
-
supporting information
p. 12938 - 12942
(2013/10/01)
-
- Diastereodivergent synthesis of trisubstituted alkenes through protodeboronation of allylic boronic esters: Application to the synthesis of the californian red scale beetle pheromone
-
E-allylic boronic esters undergo a highly diastereoselective protodeboronation with TBAF·3 H2O to give Z-trisubstituted alkenes. The selectivity can be switched to give predominantly the E-alkene instead by using KHF2/TsOH (see scheme). The utility of the methodology has been illustrated in a short synthesis of a component of the sex pheromone of the Californian red scale beetle. Copyright
- Hesse, Matthew J.,Butts, Craig P.,Willis, Christine L.,Aggarwal, Varinder K.
-
supporting information
p. 12444 - 12448
(2013/02/23)
-
- Pheromone synthesis. Part 249: Syntheses of methyl (R,E)-2,4,5- tetradecatrienoate and methyl (2E,4Z)-2,4-decadienoate, the pheromone components of the male dried bean beetle, Acanthoscelides obtectus (Say)
-
The enantiomers of methyl (E)-2,4,5-tetradecatrienoate (1), a component of the male pheromone of Acanthoscelides obtectus, were synthesized from the enantiomers of 1-undecyn-3-ol (6), which were obtained via asymmetric acetylation of (±)-1-trimethylsilyl-1-undecyn-3-ol (4) with vinyl acetate as catalyzed by lipase PS (Amano). The ortho ester Claisen rearrangement of 6 with triethyl orthoacetate was the key-step to generate the chiral allenic system. A new synthesis of (±)-1 was also executed starting from (±)-6. Three different syntheses of methyl (2E,4Z)-2,4-decadienoate (2), another component of the male pheromone of A. obtectus, were achieved by means of either palladium-catalyzed Heck reaction or a Claisen and an Al 2O3 catalyzed thermal rearrangements.
- Mori, Kenji
-
experimental part
p. 1936 - 1946
(2012/04/10)
-
- Influence of the acetylenic substituent on the intramolecular carbolithiation of alkynes
-
The intramolecular carbolithiation of a series of propargylic ethers has been performed to evaluate the influence of the terminal substituent on the efficiency and the stereochemical outcome of the cyclization. Our results show that only 5-exo-dig cyclizations are observed, and dihydrobenzofurans are obtained exclusively. Depending on the nature of the terminal substituent, two cases can be considered. If the terminal substituent carried by the acetylenic carbon atom is itself a carbon atom, the cyclization can occur provided the terminal propargylic position bears a coordinating element and is at least disubstituted. When the cyclization occurs, it follows an anti-carbolithiation pathway and thus leads to the E isomer of the exocyclic double bond. Only in one case (Ph) was a mixture of the E and Z isomers of the resulting olefin recovered. The cyclization can also take place if the alkyne is directly substituted by S or Si, provided the cyclization conditions are tuned. In the case of the trimethylsilyl substituent, a syn-carbolithiation was observed. If the double bond is recovered, in most cases, in the exocyclic position, the products can aromatize directly for SPh-substituted substrate 24. Furthermore, in the two latter cases, when alkylation of the vinyllithium intermediate is performed, isomerization of the double bond seems instantaneous. Copyright
- Girard, Anne-Lise,Lhermet, Rudy,Fressigne, Catherine,Durandetti, Muriel,Maddaluno, Jacques
-
scheme or table
p. 2895 - 2905
(2012/06/29)
-
- A mild and highly efficient method for the preparation of silyl ethers using Fe(HSO4)3/Et3N by chlorosilanes
-
Avery efficient and mild procedure for preparation of silyl ethers from benzylic, allylic, propargilic alcohols, phenols, naphtoles and some of phenolic drugs with trimethylsilylchloride (TMSCl), triethylsilylchloride (TESCl) and t-buthyldimethylsilyl chloride (TDSCl) ethers in the presence of Fe(HSO 4)3/Et3N in roomtemperature in excellent yields is reported. This procedure also allows the excellent selectivity for silylation of alcohols and phenols.
- Abri, Abdolreza,Assadi, Mohammad Galeh,Pourreza, Samira
-
p. 1449 - 1454
(2013/03/13)
-
- Aryl- or Heteroaryl-Substituted Benzene Compounds
-
The present invention relates to aryl- or heteroaryl-substituted benzene compounds. The present invention also relates to pharmaceutical compositions containing these compounds and methods of treating cancer by administering these compounds and pharmaceutical compositions to subjects in need thereof. The present invention also relates to the use of such compounds for research or other non-therapeutic purposes.
- -
-
Page/Page column 160
(2012/10/23)
-
- Stereoselective anti-SN2′ Mitsunobu reaction of α-hydroxy-α-alkenylsilanes
-
A novel silyl group-directed anti-SN2′ reaction of allylic alcohols under Mitsunobu reaction conditions is described. The Mitsunobu reaction of α-hydroxy-α-alkenylsilanes with a TBS or TIPS group gave the anti-SN2′ product, in which regio- and stereochemical outcomes of the reaction depended on the steric bulkiness of the silyl group.
- Higashino, Masato,Ikeda, Naoko,Shinada, Tetsuro,Sakaguchi, Kazuhiko,Ohfune, Yasufumi
-
supporting information; experimental part
p. 422 - 425
(2011/03/21)
-