- Strictly regio- and stereo-controlled α-alkenylation of bicyclic enone derivatives via palladium-catalyzed cross coupling and its application to a formal synthesis of (±)-carbacyclin
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A formal synthesis of carbacylin was achieved by preparing a known advanced intermediate 15 via Zr-promoted enyne bicyclization-carbonylation, Pd-catalyzed α-alkenylation of bicyclic enones, and conjugate reduction.
- Negishi, Ei-ichi,Pour, Milan,Cederbaum, Frederik E.,Kotora, Martin
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Read Online
- Towards the total synthesis of octalactin A
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In the course of a total synthesis of octalactin A, the (C1-C7) and (C8- C15) sub-units have been built up using catalytic asymmetric reactions; specifically, an asymmetric Shi epoxidation and a vinylogous Mukaiyama-aldol reaction.
- Bluet, Guillaume,Campagne, Jean-Marc
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Read Online
- Asymmetric reductive cyclization using the intramolecular conjugate addition of enolates onto α,β-unsaturated sulfoxides
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Li(sec-Bu)3BH-mediated reductive cyclization of optically pure 8-(S)- p-tolylsulfinyl)-(2E,7Z)-octadienoate 9 and 7-(p-tolylsulfinyl)-2,6- heptadienoate 16 afforded trans-2-(p-tolylsulfinyl)-methyl)cyclohexane-1- carboxylate and trans-2(p-tolyl
- Yoshizaki, Hiroki,Tanaka, Tadashi,Yoshii, Eiichi,Koizumi, Toru,Takeda, Kei
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Read Online
- Activation of 7-Endo over 6-Exo Epoxide Openings. Synthesis of Oxepane and Tetrahydropyran Systems
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Activation of 7-endo over 6-exo hydroxy epoxide opening by placement of an electron-rich double bond furthest away from the hydroxyl group leads to a reliable entry into trans- and cis-substituted oxepane systems.The scope and limitations of the method are discussed and extensions to bicyclic systems are presented.
- Nicolaou, K. C.,Prasad, C. V. C.,Somers, P. K.,Hwang, C.-K.
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Read Online
- Enantioselective Synthesis of Medium-Sized-Ring Lactones via Iridium-Catalyzed Z-Retentive Asymmetric Allylic Substitution Reaction
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Medium-sized rings are important structural units, but their synthesis, especially in a highly enantioselective manner, has been a great challenge. Herein we report an enantioselective synthesis of medium-sized-ring lactones by an iridium-catalyzed Z-retentive asymmetric allylic substitution reaction. The reaction features mild conditions and a broad substrate scope. Various eight- to 11-membered-ring lactones can be afforded in moderate to excellent yields (up to 88%) and excellent enantioselectivity (up to 99% ee). The utilization of both Z-allyl precursors and an Ir catalyst is critical for the medium-sized-ring formation.
- Ding, Lu,Song, Hao,Zheng, Chao,You, Shu-Li
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supporting information
p. 4770 - 4775
(2022/03/27)
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- Diethylzinc-Mediated Radical 1,2-Addition of Alkenes and Alkynes
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A novel diethylzinc-mediated radical 1,2-addition of perfluoroalkyl iodides to unactivated alkenes and alkynes is presented, which demonstrates a novel way to generate an ethyl difluoroacetate radical. This method is highly efficient and gives full conversions of the substrates, high yields of the products, and negligible byproducts and requires no column chromatography purifications. The mild conditions enable this protocol to exhibit excellent functional group compatibility.
- Li, Xin,He, Songtao,Song, Qiuling
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supporting information
p. 2994 - 2999
(2021/05/04)
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- Dictating Thermodynamic Control through Tethering: Applications to Stereoselective Bis-Spiroketal Synthesis
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Approaches to stereocontrol that invoke thermodynamic control fail when two or more potential products are energetically similar, but rational structural perturbations can be employed to break the energetic degeneracy and provide selective transformations. This manuscript illustrates that tethering is an effective approach for the stereoselective construction of bis-spiroketals with thermodynamically similar stereoisomers, providing a new approach to set remote stereocenters and prepare complex structures that have not previously been accessed stereoselectively.
- Asari, Austin H.,Floreancig, Paul E.
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supporting information
p. 6622 - 6626
(2020/03/04)
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- Stereoselective Csp3?Csp2 Cross-Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides
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We report palladium-catalyzed cross-coupling reactions of chiral secondary non-stabilized dialkylzinc reagents, prepared from readily available chiral secondary alkyl iodides, with alkenyl and aryl halides. This method provides α-chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76 % for 3 reaction steps). The configurational stability of these chiral non-stabilized dialkylzinc reagents was determined and exceeded several hours at 25 °C. DFT calculations were performed to rationalize the stereoretention during the catalytic cycle. Furthermore, the cross-coupling reaction was applied in an efficient total synthesis of the sesquiterpenes (S)- and (R)-curcumene with control of the absolute stereochemistry.
- Skotnitzki, Juri,Kremsmair, Alexander,Keefer, Daniel,Gong, Ye,de Vivie-Riedle, Regina,Knochel, Paul
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supporting information
p. 320 - 324
(2019/11/26)
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- Iodinated Choline Transport-Targeted Tracers
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We present a novel series of radioiodinated tracers and potential theranostics for diseases accompanied by pathological function of proteins involved in choline transport. Unlike choline analogues labeled with 11C or 18F that are currently used in the clinic, the iodinated compounds described herein are applicable in positron emission tomography, single-photon emission computed tomography, and potentially in therapy, depending on the iodine isotope selection. Moreover, favorable half-lives of iodine isotopes result in much less challenging synthesis by isotope exchange reaction. Six of the described compounds were nanomolar ligands, and the best compound possessed an affinity 100-fold greater than that of choline. Biodistribution data of 125I-labeled ligands in human prostate carcinoma bearing (PC-3) mice revealed two compounds with a biodistribution profile superior to that of [18F]fluorocholine.
- ?vec, Pavel,Novy, Zbyněk,Ku?ka, Jan,Pet?ík, Milo?,Sedlá?ek, Ond?ej,Kucha?, Martin,Li?ková, Barbora,Medvedíková, Martina,Kolouchová, Kristyna,Groborz, Ond?ej,Loukotová, Lenka,Konefa?, Rafa? ?.,Hajdúch, Marián,Hruby, Martin
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supporting information
p. 15960 - 15978
(2020/12/23)
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- Lewis Acid Catalyzed Electrophilic Aminomethyloxygenative Cyclization of Alkynols with N, O-Aminals
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Lewis acid enables the electrophilic carbooxygenative cyclization of alkynols with N,O-aminals. The new process proceeds efficiently under very mild conditions via a pathway that is opposite to classical carbo-metalation. These reactions exhibit broad substrate generality and functional group compatibility, leading to a wide variety of 5-8-membered oxacycles bearing diverse functional groups. The cyclization products can be elaborated via simple functional group transformations to generate synthetically useful oxacycles.
- Chen, Anrong,Yu, Houjian,Yan, Jiaqi,Huang, Hanmin
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supporting information
p. 755 - 759
(2020/01/28)
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- Enantioselective Aza-Heck Cyclizations of N-(Tosyloxy)carbamates: Synthesis of Pyrrolidines and Piperidines
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Pd(0)-systems modified with SPINOL-derived phosphoramidate ligands promote highly enantioselective aza-Heck cyclizations of alkenyl N-(tosyloxy)carbamates. The method provides versatile access to challenging N-heterocycles and represents the broadest scope enantioselective aza-Heck protocol developed to date.
- Ma, Xiaofeng,Hazelden, Ian R.,Langer, Thomas,Munday, Rachel H.,Bower, John F.
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supporting information
p. 3356 - 3360
(2019/03/07)
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- Regioselective Gold-Catalyzed Hydration of CF3- and SF5-alkynes
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The regioselective gold-catalyzed hydration of CF3- and SF5-alkynes is described. The corresponding trifluoromethylated and pentasulfanylated ketones are obtained in up to 91% yield as single regioisomers showcasing the use of CF3 and SF5 as highly efficient directing groups in this reaction. Notably, this transformation represents the first use of CF3- and SF5-alkynes in gold catalysis.
- Cloutier, Mélissa,Roudias, Majdouline,Paquin, Jean-Fran?ois
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supporting information
p. 3866 - 3870
(2019/05/24)
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- Regioselectivity Influences in Platinum-Catalyzed Intramolecular Alkyne O-H and N-H Additions
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The steric and electronic drivers of regioselectivity in platinum-catalyzed intramolecular hydroalkoxylation are elucidated. A branch point is found that divides the process between 5-exo and 6-endo selective processes, and enol ethers can be accessed in good yields for both oxygen heterocycles. The main influence arises from an electronic effect, where the alkyne substituent induces a polarization of the alkyne that leads to preferential heteroatom attack at the more electron-deficient carbon. The electronic effects are studied in other contexts, including hydroacyloxylation and hydroamination, and similar trends in directionality are predominant although not uniformly observed.
- Costello, Jeff P.,Ferreira, Eric M.
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supporting information
p. 9934 - 9939
(2019/12/24)
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- Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide
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An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO2 has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.
- Chen, Yue-Gang,Shuai, Bin,Ma, Cong,Zhang, Xiu-Jie,Fang, Ping,Mei, Tian-Sheng
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supporting information
p. 2969 - 2972
(2017/06/07)
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- Radical Hydrodeiodination of Aryl, Alkenyl, Alkynyl, and Alkyl Iodides with an Alcoholate as Organic Chain Reductant through Electron Catalysis
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A simple and efficient method for radical hydrodeiodination is reported. The novel approach uses electron catalysis. In situ generated Na-alcoholates are introduced as radical chain reducing reagents and reactions work with O2as cheap initiator. Hydrodeiodination works on aryl, alkenyl, alkynyl iodides and a tert-alkyl iodide also gets reduced applying the method. Albeit less general, the method is also applicable to the reduction of aryl bromides. The novel reagent is successfully used to conduct typical reductive radical cyclization reactions and mechanistic studies are reported.
- Dewanji, Abhishek,Mück-Lichtenfeld, Christian,Studer, Armido
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supporting information
p. 6749 - 6752
(2016/06/09)
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- Tandem Gold-Catalyzed Dehydrative Cyclization/Diels-Alder Reactions: Facile Access to Indolocarbazole Alkaloids
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A gold-catalyzed synthesis of cyclic 2-oxodienes from readily prepared propargyl alcohols and the subsequent Diels-Alder reaction are reported. The dehydrative cyclization reactions proceeded smoothly, and the dienes formed in situ were demonstrated to un
- Borrero, Nicholas V.,Deratt, Lindsey G.,Ferreira Barbosa, Lais,Abboud, Khalil A.,Aponick, Aaron
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supporting information
p. 1754 - 1757
(2015/04/14)
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- Gold-Catalyzed Rearrangement of Alkynyl Donor-Acceptor Cyclopropanes to Construct Highly Functionalized Alkylidenecyclopentenes
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A gold-catalyzed 1,7-addition-cyclization-elimination cascade sequence performed on a range of alkynyl-substituted donor-acceptor-type cyclopropanes provides facile entry to highly functionalized exo-alkylidenecyclopentenes under very mild conditions. Iso
- Chen, Huiyu,Zhang, Jing,Wang, David Zhigang
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supporting information
p. 2098 - 2101
(2015/05/13)
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- Leveraging the micellar effect: Gold-catalyzed dehydrative cyclizations in water at room temperature
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The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings can be significantly decreased.
- Minkler, Stefan R. K.,Isley, Nicholas A.,Lippincott, Daniel J.,Krause, Norbert,Lipshutz, Bruce H.
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supporting information
p. 724 - 726
(2014/03/21)
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- Non-Pd transition metal-catalyzed hydrostannations: Bu3SnF/PMHS as a tin hydride source
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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.
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p. 4000 - 4008
(2013/06/27)
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- Approach to the functionalized cyclopentane core of marine prostanoids by applying a radical cyclization of β-disubstituted acrylates
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A synthetic approach to highly functionalized cyclopentanes that incorporate adjacent secondary and tertiary alcohols is described. These systems, prepared in one step by a ketyl radical cyclization of β-disubstituted acrylates, represent the core of the marine prostanoid family of natural products. The Royal Society of Chemistry.
- Hong, Lisa P. T.,Chak, Christopher,Donner, Christopher D.
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supporting information
p. 6186 - 6194
(2013/09/12)
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- Design and synthesis of a class of twin-chain amphiphiles for self-assembled monolayer-based electrochemical biosensor applications
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A new class of twin-chain hydroxyalkylthiols (mercaptoalkanols) is described that features a nearly constant cross section and the potential for modification at one or both termini. These compounds are regioselectively available through Pd-mediated coupli
- Fisher, Thomas J.,Canete, Socrates Jose P.,Lai, Rebecca Y.,Dussault, Patrick H.
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p. 3263 - 3270
(2013/07/05)
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- Investigation of the origin and synthetic application of the pseudodilution effect for Pd-catalyzed macrocyclisations in concentrated solutions with immobilized catalysts
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Immobilized Pd-complexes allowed macrocyclisations via the Tsuji-Trost-reaction in concentrated solutions. Systematic studies suggest that the origin of this pseudodilution effect is neither film diffusion nor gel diffusion, but the reduction in conformational freedom of intermediates and intramolecular prenucleophile activation. In contrast a pseudodilution effect could not be observed for Sonogashira- and Suzuki-macrocyclisations.
- Brehm, Elisabeth,Breinbauer, Rolf
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supporting information
p. 4750 - 4756
(2013/07/26)
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- E-SELECTIN ANTAGONISTS
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Compounds, compositions and methods are provided for inhibiting in vitro and in vivo processes mediated by E-selectin binding. More specifically, particular glycomimetic compounds are described, wherein the compounds are E- selectin antagonists.
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Page/Page column 43-44
(2012/04/04)
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- Cyclization strategies to polyenes using Pd(II)-catalyzed couplings of pinacol vinylboronates
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As a complement to Pd(0)-catalyzed cyclizations, seven Pd(II)-catalyzed cyclization strategies are reported. α,ω-Diynes are selectively hydroborated to bis(boronate esters), which cyclize under Pd(II)-catalysis producing a diverse array of small, medium,
- Iafe, Robert G.,Chan, Daniel G.,Kuo, Jonathan L.,Boon, Byron A.,Faizi, Darius J.,Saga, Tomomi,Turner, Jonathan W.,Merlic, Craig A.
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supporting information; experimental part
p. 4282 - 4285
(2012/10/07)
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- Synthesis of bridged inside-outside bicyclic ethers through oxidative transannular cyclization reactions
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The classical geometry of the 6-endo transition state for nucleophilic additions into oxocarbenium ions can be perturbed by incorporating the reactive groups into medium-sized rings, leading to the formation of 2,6-trans-dialkyl tetrahydropyrans. The bicy
- Han, Xun,Floreancig, Paul E.
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supporting information; scheme or table
p. 3808 - 3811
(2012/09/08)
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- Microwave assisted synthesis of bridgehead alkenes
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A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels-Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter
- Cleary, Leah,Yoo, Hoseong,Shea, Kenneth J.
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supporting information; experimental part
p. 1781 - 1783
(2011/06/16)
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- Stereoselective synthesis of (+)-euphococcinine and (-)-adaline
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(Chemical Equation Presented) We describe the syntheses of (+)-euphococcinine and (-)-adaline, two naturally occurring alkaloids containing a quaternary carbon bearing a nitrogen atom. Key features of the syntheses are a 3,3-sigmatropic rearrangement to give an all-carbon quaternary center, a ring-closing alkene metathesis to give an 8-membered ring, and the use of a single enantiomer of p-menthane-3-carboxaldehyde to make two natural alkaloids of opposite configuration.
- Arbour, Melissa,Roy, Stephanie,Godbout, Cedrickx,Spino, Claude
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supporting information; experimental part
p. 3806 - 3814
(2009/09/25)
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- β-Iodoallenolates as springboards for annulation reactions
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β-Iodoallenolates II, generated from alkynones I with tetra-n-butylammonlum iodide and a Lewis acid, underwent selective single or double annulation, depending on the Lewis acid promoter. Treatment with TiCl4 gave cyclohexenyl alcohols III, whe
- Ciesielski, Jennifer,Canterbury, Daniel P.,Frontier, Alison J.
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supporting information; experimental part
p. 4374 - 4377
(2009/12/24)
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- Formal total synthesis of RK-397 via an asymmetric hydration and iterative allylation strategy
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(Chemical Equation Presented) A formal total synthesis of the oxopentaene macrolide antibiotic RK-397 has been achieved. Nine stereocenters were established by a combination of allylation and our asymmetric hydration reactions and a 1,5-anti-selective ald
- Guo, Haibing,Mortensen, Matthew S.,O'Doherty, George A.
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supporting information; experimental part
p. 3149 - 3152
(2009/05/11)
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- Enantioselective total synthesis of pyrinodemin A
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Pyrinodemin A 1, a cytotoxic marine alkaloid, was synthesized in a convergent and enantioselective fashion. The key steps are an asymmetric intramolecular dipolar cycloaddition of an oxazoline N-oxide to introduce the bicyclic ring system of the molecule, a cuprate coupling for the extension of the saturated chain and a B-alkyl Suzuki coupling for the introduction of a 3-pyridyl moiety. Reductive amination allowed the coupling of the second side-chain onto the nitrogen atom to give 1. Additionally, attempts to prepare 1 from a trienic precursor by a double B-alkyl Suzuki reaction are described. The Royal Society of Chemistry.
- Pouilhes, Annie,Amado, Anel Flores,Vidal, Anne,Langlois, Yves,Kouklovsky, Cyrille
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scheme or table
p. 1502 - 1510
(2008/10/09)
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- Solid-phase synthesis of [5.5]-spiroketals
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An efficient and reliable multi-step synthesis of 251 natural product-like [5.5]-spiroketals on solid supports has been developed. As central key step, a double intramolecular hetero-Michael (DIHMA) reaction to alkynones was applied. The sequence allows for introduction of numerous substituents on the scaffold and for variation of stereochemistry. [5.5]-Spiroketals bearing an additional ketone were obtained in high overall yields. Further diversification was achieved by reduction of the ketone and reductive amination using polymer-supported borohydride, Grignard reaction and conversion to oxime derivatives in the solution phase.
- Sommer, Stefan,Kuehn, Marc,Waldmann, Herbert
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supporting information; experimental part
p. 1736 - 1750
(2009/08/14)
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- DBU-promoted facile, chemoselective cleavage of acetylenic TMS group
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Acetylenic trimethylsilyl (TMS) groups were efficiently removed using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). With either 1.0 or even 0.1 equivalents of DBU, smooth desilylation of various terminal acetylenic TMS groups was accomplished selectively in the presence of alkyl silyl ethers and other base-labile groups. Furthermore, more sterically hindered terminal acetylenic silyl groups such as TBDMS and TIPS remained intact under these conditions. Georg Thieme Verlag Stuttgart.
- Yeom, Chang-Eun,Mi, Jeong Kim,Choi, Whail,Kim, B. Moon
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p. 565 - 568
(2008/12/22)
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- Design, synthesis and biological evaluations of a novel series of enediynes constituted with DNA cleavage, alkylating and DNA binding agents via varies spacers
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Among the three series of complicated combinatory enediynes, 3a-d were more active than 2a-c and 4a-b, in which 3a-b showed equally inhibitory activity against the growth of Hepa59T/VGH, KB and Hela with mean IC50 values lower than 10 μg/mL. Co
- Linb, Chi-Fong,Hwanga, Martin,Kuo, Yao-Haur,Wu, Ming-Jung
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p. 525 - 532
(2008/02/11)
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- Palladium(0)-catalyzed Suzuki-Miyaura cross-coupling reactions of potassium aryl- and heteroaryltrifluoroborates with alkenyl bromides
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Efficient palladium(0)-catalyzed Suzuki-Miyaura cross-couplings are described. The reactions involving potassium aryl- and heteroaryltrifluoroborates with alkenyl bromides can generally be carried out using ≤2 mol % of palladium catalyst and 3 equiv of ba
- Molander, Gary A.,Fumagalli, Tiziano
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p. 5743 - 5747
(2007/10/03)
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- Palladium(0)-catalyzed synthesis of chiral ene-allenes using alkenyl trifluoroborates
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Enantioenriched allenes serve as chiral transfer reagents, making them attractive synthetic targets. Herein, the synthesis of enantioenriched allenes utilizing a Pd(0)-catalyzed cross-coupling reaction of propargylic carbonates and phosphates with alkenyl trifluoroborates is reported. Di-, tri-, and tetrasubstituted allenes were synthesized in moderate to high optical yields. Several racemic allenes possessing various functional groups were also synthesized.
- Molander, Gary A.,Sommers, Erin M.,Baker, Sharon R.
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p. 1563 - 1568
(2007/10/03)
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- 2,3,4-Substituted cyclopentanones as therapeutic agents
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Disclosed herein are compounds comprising or a pharmaceutically acceptable salt or a prodrug thereof, wherein a dashed line represents the presence or absence of a bond; Y is a carboxylic acid, sulfonic acid, or phosphonic acid functional group; or an amide or ester thereof comprising from 0 to 12 carbon atoms; or Y is hydroxymethyl or an ether thereof comprising from 0 to 12 carbon atoms; or Y is a tetrazolyl functional group; A is —(CH2)6—, cis —CH2—CH═CH—(CH2)3—, or —CH2—C≡C—(CH2)3— wherein 1 or 2 carbons may be substituted with S or O; B is hydrogen, C1-6 hydrocarbyl, CN, CO2H, or —(CH2)mX(CH2)pH, wherein m is at least 1 and the sum of m and p is from 1 to 5; X is S or O; J is H, CH3, or CF3; D is a covalent bond, CH2, O, or S; and E is an aromatic heterobicyclic ring system which may have substituents comprising up to 6 non-hydrogen atoms each. Methods, compositions, and medicaments related thereto are also disclosed.
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Page/Page column 17; sheet 3
(2010/11/30)
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- Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant
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A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.
- Izawa, Yusuke,Shimizu, Isao,Yamamoto, Akio
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p. 2033 - 2045
(2007/10/03)
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- 10,10-DIALKYL PROSTANOIC ACID DERIVATIVES AS AGENTS FOR LOWERING INTRAOCULAR PRESSURE
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The present invention provides a method of treating ocular hypertension or glaucoma which comprises administering to an animal having ocular hypertension or glaucoma therapeutically effective amount of a compound represented by the general formula I; wherein the dashed line indicates the presence or absence of a bond, the hatched wedge indicates the α (down) configuration, and the solid triangle indicates the β (up) configuration; B is a single, double, or triple covalent bond; n is 0-6; X is CH2, S or O; Y is any pharmaceutically acceptable salt of CO2H, or CO2R, CONR2, NHCH2CH2OH, N(CH2CH2OH)2, CH2OR, P(O)(OR)2, CONRSO2R, SONR2, or R is H, C1-6 alkyl or C2-6 alkenyl; R2 and R3 are C1-6 linear alkyl which may be the same or different, and may be bonded to each other such that they form a ring incorporating the carbon to which they are commonly attached; R4 is hydrogen, R, C(═O)R, or any group that is easily removed under physiological conditions such that R4 is effectively hydrogen; R5 is hydrogen or R; R6 is iv) hydrogen; v) a linear or branched hydrocarbon containing between 1 and 8 carbon atoms, which may contain one or more double or triple bonds, or oxygen or halogen derivatives of said hydrocarbon, wherein 1-3 carbon or hydrogen atoms may be substituted by O or a halogen; or vi) aryloxy, heteroaryloxy, C3-8 cycloalkyloxy, C3-8 cycloalkyl, C6-10 aryl or C3-10 heteroaryl, wherein one or more carbons is substituted with N, O, or S; and which may contain one or more substituents selected from the group consisting of halogen, trihalomethyl, cyano, nitro, amino, hydroxy, C6-10 aryl, C3-10 heteroaryl, aryloxy, heteroaryloxy, C1-6 alkyl, OR, SR, and SO2R. Some of the compounds of the present invention and some of their methods of preparation are also novel an nonobvious.
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- Benzopyran or thiobenzopyran derivatives
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The present invention provides novel benzopyran compounds, pharmaceutically acceptable salts thereof and stereoisomers thereof where the benzopyran compounds of the invention are compounds according to Formula I: The present invention further provides pharmaceutical compositions which possess anti-estrogenic activity and comprise at least one benzopyran compound of the invention and a method of treating breast cancer by administration of an effective amount of a benzopyran compound provided by the present invention.
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Page/Page column 194-195
(2010/01/31)
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- Cascade polycyclization: Exploration of a convergent route to access various tricyclic and tetracyclic products related to sterols
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The expedient synthesis of tricyclic and tetracyclic compounds via a cascade polycyclization methodology is described. Nazarov substrates (II) containing two Michael acceptors and a cyclohexenone ester (I) underwent cycloaddition followed by intramolecula
- Guay, Benoit,Deslongchamps, Pierre
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p. 6140 - 6148
(2007/10/03)
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- Synthesis of a macroheterocyclic compound through photodecarboxylation of potassium ω-phthalimidoalkynoate
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A macroheterocyclic alkyne compound is prepared through photodecarboxylation of ω-phthalimidoalkynoates in moderate yield.
- Yoo, Dong Jin,Kim, Eun Young,Oelgem?ller, Michael,Shim, Sang Chul
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p. 1049 - 1055
(2007/10/03)
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- Regioselective palladium-catalyzed cross-coupling reactions in the synthesis of novel 2,3-disubstituted thiophene derivatives
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A reactivity optimization study of the palladium-catalyzed cross-coupling reactions of 2,3-dibromothiophene and organometallic reagents has been conducted. Regioselective coupling at the C2 position, accomplished most notably by Suzuki coupling, was combined with a Stille reaction at C3 using Fu's modification, to afford the 2,3-disubstituted thiophene derivatives.
- Pereira, Raquel,Iglesias, Beatriz,De Lera, Angel R
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p. 7871 - 7881
(2007/10/03)
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- An enantioselective synthesis of benzylidene-protected syn-3,5-dihydroxy carboxylate esters via osmium, palladium, and base catalysis
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(matrix presented) The enantioselective syntheses of several protected syn-3,5-dihydroxy carboxylic esters have been achieved from the corresponding achiral 1,3-dieneoates The route relies upon an enantio- and regioselective Sharpless dihydroxylation and
- Hunter, Thomas J.,O'Doherty, George A.
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p. 1049 - 1052
(2007/10/03)
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- New developments in asymmetric Bradsher cycloadditions: Use of chiral dienes
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Several serinol derivatives have been prepared and condensed following the Zincke reaction with 2,7-naphthyridine. The resulting naphthyridinium salts were engaged in Bradsher cycloadditions with enol ethers and afforded tetracyclic adducts, potential synthetic precursors of manzamine A alkaloid. (C) 2000 Elsevier Science Ltd.
- Urban,Duval,Langlois
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p. 9251 - 9256
(2007/10/03)
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- Bis(oxazoline) and bis(oxazolinyl)pyridine copper complexes as enantioselective Diels-Alder catalysts: Reaction scope and synthetic applications
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The scope of the Diels-Alder reaction catalyzed by bis(oxazoline) copper complexes has been investigated. In particular, [Cu((S,S)-t-Bu-box)](SbF6)2 (1b) has been shown to catalyze the Diels-Alder reaction between 3-propenoyl- 2-oxaz
- Evans, David A.,Barnes, David M.,Johnson, Jeffrey S.,Lectka, Thomas,Von Matt, Peter,Miller, Scott J.,Murry, Jerry A.,Norcross, Roger D.,Shaughnessy, Eileen A.,Campos, Kevin R.
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p. 7582 - 7594
(2007/10/03)
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- ANTAGONISTS OF GONADOTROPIN RELEASING HORMONE
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There are disclosed compounds of formula (I) STR1 and pharmaceutically acceptable salts thereof which are useful as antagonists of GnRH and as such may be useful for the treatment of a variety of sex-hormone related and other conditions in both men and women.
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- Synthesis of β-Resorcylic Macrolides via Organopalladium Chemistry. Application to the Total Synthesis of (S)-Zearalenone
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The β-resorcyclic macrolides are a class of naturally occurring 12- and 14-membered macrolides.Zearalenone (1), a 14-membered macrolide of this type, displays useful biological activity, which has led to great synthetic interest.In this paper the intramolecular coupling reaction of an organostannane with an electrophile is used to construct β-resorcylic macrolides.The intramolecular coupling of an aryl iodide with a vinylstannane provided the highest yield of lactones.This methodology was then used to prepare (S)-zearalenone (1).
- Kalivretenos, A.,Stille, J. K.,Hegedus, L. S.
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p. 2883 - 2894
(2007/10/02)
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- Synthesis of 19,19,20,20,20-Pentadeuteriolipoxin A4 Methyl Ester and 19,19,20,20,20-Pentadeuterioarachidonic Acid. Agents for Use in the Quantitative Detection of Naturally Occurring Eicosanoids
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19,19,20,20,20-Pentadeuteriolipoxin A4 methyl ester (2) was synthesized from key intermediates 31 and 32. 19,19,20,20,20-Pentadeuterioarachidonic acid (1) and its methyl ester (24) were also synthesized by sequential coupling of intermediates 1
- Marron, B.E.,Spanevello, R.A.,Elisseou, M.E.,Serhan, C.N.,Nicolaou, K.C.
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p. 5522 - 5527
(2007/10/02)
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