- An efficient synthesis of alkyl α-(hydroxymethyl)acrylates induced by DABCO in an aqueous medium
-
Alkyl α-(hydroxymethyl)acrylates are prepared in high yields on a synthetic scale by hydroxymethylation of the corresponding acrylates using 30% aqueous formaldehyde in THF or DME as solvent and DABCO as the catalyst.
- Turki, Taoufik,Villiéras, Jean,Amri, Hassen
-
-
Read Online
- Stereoselective Modification of N-(α-Hydroxyacyl)-glycinesters via Palladium-Catalyzed Allylic Alkylation
-
N-(α-Hydroxyacyl)-glycinesters can be used as excellent nucleophiles in Pd-catalyzed allylic alkylation. The method allows for the stereoselective introduction of a wide range of side chains, including highly functionalized ones. Both diastereomers can be accessed through variation of the reaction conditions. Furthermore, the use of stannylated carbonates introduces vinylstannane motifs, which are eligible for subsequent C-C coupling reactions.
- Horn, Alexander,Kazmaier, Uli
-
-
Read Online
- Iterative Synthesis of Polydeoxypropionates Based on Iridium-Catalyzed Asymmetric Hydrogenation of α-Substituted Acrylic Acids
-
A novel iterative protocol for the synthesis of polydeoxypropionates was developed based on iridium-catalyzed asymmetric hydrogenation of α-substituted acrylic acids. The catalyst loading can be as low as 0.01 mol %, and the overall yield for one iterativ
- Che, Wen,Wen, Danyang C.,Zhu, Shou-Fei,Zhou, Qi-Lin
-
-
Read Online
- Convenient general asymmetric synthesis of roche ester derivatives through catalytic asymmetric hydrogenation: Steric and electronic effects of ligands
-
An efficient and concise asymmetric hydrogenation of acrylate esters promoted by the cationic ruthenium monohydride complex [Ru(H) (hη6-cot)SYNPHOS]+BF44- is reported. A full investigation of the effects of catalyst precursors, solvents, temperature, hydrogen pressure, substrates as well as steric and electronic properties of ligands was carried out. The corresponding valuable Roche ester derivatives were obtained in good to excellent isolated yields and high enantioselectivities under mild conditions. The robustness and practicability of this highly enantioselective hydrogenation was demonstrated by the synthesis of the 3-hydroxy-2-methylpropanoic acid tert-butyl ester on a multigram scale, resulting in excellent yield and ee up to 94%.
- Pautigny, Cyrielle,Jeulin, Severine,Ayad, Tahar,Zhang, Zhaoguo,Genet, Jean-Pierre,Ratovelomanana-Vidal, Virginie
-
-
Read Online
- Total synthesis and absolute configuration of curvularides A-E
-
The first total synthesis of curvularides A-E, isolated from a culture broth of the endophytic fungus Curvularia geniculata, is described. The divergent total synthesis reported herein confirmed the absolute configurations of curvularides A-E and supported that these natural products might be obtained from a common biosynthetic pathway. The key steps involved in the synthesis were the diastereoselective hydrogenation of exo-methylene-γ-butyrolactone to α-methyl-γ-butyrolactone, Sharpless kinetic resolution, Sharpless asymmetric epoxidations, and intramolecular and intermolecular epoxide openings.
- Sudhakar, Gangarajula,Satish, Kovela,Raghavaiah, Jakka
-
-
Read Online
- Total Synthesis of Clavilactone B: A Radical Cyclization-Fragmentation Strategy
-
A new synthetic route to clavilactone B, a naturally occurring inhibitor of epidermal growth factor receptor (EGFR) tyrosine kinase, is disclosed. The route features a sequential samarium-mediated radical cyclization-fragmentation of an indanone derivativ
- Suizu, Hiroshi,Shigeoka, Daisuke,Aoyama, Hiroshi,Yoshimitsu, Takehiko
-
-
Read Online
- Effect of Lewis acids and low temperature initiators on the allyl transfer reaction involving phthalimido-N-oxyl radical
-
Previously, we reported allyl transfer reactions of allyl bromide and allyl phthalimido-N-oxyl substrates with hydrocarbons that result in CC bond formation. In both cases, efficient chain transfer processes along with high reaction yields were observed. Since PINO chemistry leads to an environmentally friendly method of hydrocarbon functionalization, additional studies were performed in order to improve the process. To expand the utility of this reaction, we carried out experiments to optimize reaction conditions and tested the effect of Lewis acids and low temperature initiators. Although allyl-PINO substrates reacted slightly slower than the bromides, the reactions were cleaner with little or no side products. The chain lengths for these reactions were compromised at lower temperatures, attributable to the high activation energy required for the hydrogen atom abstraction by PINO. The addition of a Lewis acid catalyst (AlCl3) improves the product yield and reaction rate, possibly due to the formation of a PINO/AlCl3 complex which lowers the activation energy for hydrogen abstraction step.
- Patil, Shradha,Chen, Liang,Tanko, James M.
-
-
Read Online
- Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction
-
Abstract: We utilized the indium-mediated allylation reaction for the synthesis of carbohydrate structures containing the 3-deoxy-2-ulose motif, a barely investigated compound class. The stereoselective outcome can be controlled by the presence or absence of a chelating group in α-position to the carbonyl function. By introduction of an UV-active allyl building block, we enabled epimer separation by HPLC towards the synthesis of 3-deoxy-d-glycero-d-galacto-2-nonulose, the carboxyl-reduced analogue of widely distributed 3-deoxy-d-glycero-d-galacto-nonulosonic acid (Kdn). Ozonolysis of the introduced 2-C-methylidenepropan-1-ol motif provided the desired 3-deoxy-2-uloses. Graphical abstract: [Figure not available: see fulltext.].
- Gintner, Manuel,Denner, Christian,Schm?lzer, Christoph,Fischer, Michael,Frühauf, Peter,K?hlig, Hanspeter,Schmid, Walther
-
-
Read Online
- Metal-free access to 3-allyl-2-alkoxychromanonesviaphosphine-catalyzed alkoxy allylation of chromones with MBH carbonates and alcohols
-
A metal-free access to 3-allyl-2-alkoxychromanones by PPh3-catalyzed alkoxy allylation of chromones with MBH carbonates and alcohols is described. This reaction is performed under mild conditions and it shows good functional group tolerance, providing a series of functionalized chromanones in moderate to high yields with excellent diastereoselectivities. Deuterium-labeling experiments to probe a possible mechanism and scale-up reaction were also conducted.
- Meng, Ling,Chang, Xiaoyong,Lin, Zhenyang,Wang, Jun (Joelle)
-
-
Read Online
- N-Arylamines Coupled with Aldehydes, Ketones, and Imines by Means of Photocatalytic Proton-Coupled Electron Transfer
-
A photoredox-catalyzed umpolung strategy for coupling reactions between aldehydes, ketones, imines, and N-arylamines is reported. These reactions proceed by a Br?nsted acid-activated proton-coupled electron transfer pathway, and the protocol was used to synthesize a broad scope of 1,2-amino alcohols and vicinal diamines, both of which are common motifs in biologically active natural products, pharmaceutically active molecules, and ligands.
- Xia, Qing,Tian, Hao,Dong, Jianyang,Qu, Yi,Li, Lili,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
-
-
Read Online
- Zinc-Mediated Double Addition on Functionalized Nitriles
-
Allylzinc reagents were used to access highly functionalized tertiary carbinamine derivatives in high yields from cyanoesters and cyanocarbonates. While the monoaddition of organometallics on nitriles is generally observed, in this work the nucleophilic a
- Caillé, Julien,Pantin, Mathilde,Boeda, Fabien,Pearson-Long, Morwenna S.M.,Bertus, Philippe
-
-
Read Online
- Metal-Free C(sp3)-H Allylation via Aryl Carboxyl Radicals Enabled by Donor-Acceptor Complex
-
The first aryl carboxyl radical generation by the donor-acceptor complex with N-acyloxyphthalimides and Hantzsch esters is reported. Regio- and chemoselective C(sp3)-H bond allylation is enabled by aryl carboxyl radicals with visible light irradiation under mild and metal-free conditions.
- Li, Yang,Zhang, Jing,Li, Defang,Chen, Yiyun
-
-
Read Online
- The aqueous trimethylamine mediated Baylis-Hillman reaction
-
Aqueous trimethylamine mediated Baylis-Hillman coupling of alkyl acrylates with aldehydes is described.
- Basavaiah, Deevi,Krishnamacharyulu, Marimganti,Rao, Anumolu Jaganmohan
-
-
Read Online
- Catalytic Asymmetric Synthesis of Quaternary Barbituric Acids
-
The catalytic asymmetric α-functionalization of prochiral barbituric acids, a subtype of pseudosymmetric 1,3-diamides, to yield the corresponding 5,5-disubstituted (quaternary) derivatives remains essentially unsolved. In this study 2-alkylthio-4,6-dioxopirimidines are designed as key 1,3-diamide surrogates that perform exceedingly in amine-squaramide catalyzed C-C bond forming reactions with vinyl ketones or Morita-Baylis-Hillmann-type allyl bromides as electrophiles. Mild acid hydrolysis of adducts affords barbituric acid derivatives with an in-ring quaternary carbon in unprecedented enantioselectivity, offering valuable materials for biological evaluations.
- Del Pozo, Sandra,Vera, Silvia,Oiarbide, Mikel,Palomo, Claudio
-
-
Read Online
- Improved syntheses of ethyl α-(bromomethyl)acrylate and 2-methylene-1,3- propanediol via ethyl α-(hydroxymethyl)acrylate
-
Ethyl α-(bromomethyl)acrylate (1) and 2-methylene-1,3-propanediol (2) have been prepared via formalhedyde addition to ethyl acrylate in the presence of DABCO, giving α, β-unsaturated ester 3. Reduction of hydroxy ester 3 with one equivalent of alane, then borohydride reduction of the resulting aldehyde 4 gives 2.
- Byun,Reddy,Bittman
-
-
Read Online
- An efficient and simple strategy toward the synthesis of highly functionalized compounds
-
The expedient syntheses of small libraries of ((β-ethoxycarbonyl, -cyano and -acetyl)propyloxy) methylphosphonate scaffolds bearing olefin, sulfanyl, or amine functions are described. All these new derivatives are readily produced from easily available starting reagents (aldehydes, electron-poor olefins, and dialkylphosphites) following a three steps reaction sequence of condensations, SN2′-type reaction and a conjugated thia- or aza-Michael 1,4-addition with aromatic and aliphatic thiol or amine nucleophiles.
- Jmai, Momtez,Efrit, Mohamed Lotfi,Dubreuil, Didier,Blot, Virginie,Lebreton, Jacques,M'rabet, Hédi
-
p. 978 - 995
(2021/08/06)
-
- Copper-catalyzed radical oxyallylation of olefins for the construction of alkene-containing isoxazolines
-
A radical-mediated approach to alkene oxyallylation using allylic oximes is described. The reaction proceeds under copper-catalytic redox-neutral conditions and tolerates various functional groups. This protocol thus enables the synthesis of structurally valuable isoxazolines and the introduction of a versatile olefin motif in a single step.
- He, Xiaoxue,Qian, Lijie,Dai, Yuyu,Yan, Xinhuan,Li, Xiaoqing,Xu, Xiangsheng
-
supporting information
(2021/05/31)
-
- Phosphine-Catalyzed Cascade Annulation of MBH Carbonates and Diazenes: Synthesis of Hexahydrocyclopenta[c]pyrazole Derivatives
-
A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.
- Guo, Hongchao,Li, Hongxiang,Liu, Hao,Shi, Wangyu,Wang, Chang,Wang, Wei,Wu, Yongjun
-
supporting information
p. 5571 - 5575
(2021/07/31)
-
- Copper-Catalyzed Intermolecular Alkynylation and Allylation of Unactivated C(sp3)-H Bonds via Hydrogen Atom Transfer
-
We describe Cu-catalyzed intermolecular alkynylation and allylation of unactivated C(sp3)-H bonds with singly occupied molecular orbital-philes (SOMO-philes) via hydrogen atom transfer (HAT). Employing N-fluoro-sulfonamide as a HAT reagent, a set of subst
- Liang, Lei,Guo, Ge,Li, Chen,Wang, Song-Lin,Wang, Yue-Hui,Guo, Hai-Ming,Niu, Hong-Ying
-
supporting information
p. 8575 - 8579
(2021/11/13)
-
- Photoredox-Coupled F-Nucleophilic Addition: Allylation of gem-Difluoroalkenes
-
A novel strategy for the expedient construction of CF3-embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single-electron oxidation, electron-rich gem-difluoroalkenes, which otherwise are essentially reluctant towards F-nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α-CF3-substituted benzylic radical intermediates using cheap and readily available starting materials.
- Liu, Haidong,Ge, Liang,Wang, Ding-Xing,Chen, Nan,Feng, Chao
-
supporting information
p. 3918 - 3922
(2019/02/19)
-
- N-Heterocyclic Carbene Catalyzed (5+1) Annulations Exploiting a Vinyl Dianion Synthon Strategy
-
Direct polarity inversion of conjugate acceptors provides a valuable entry to homoenolates. N-heterocyclic carbene (NHC) catalyzed reactions, in which β-unsubstituted conjugate acceptors undergo homoenolate formation and C?C bond formation twice, have been developed. Specifically, the all-carbon (5+1) annulations give a range of mono- and bicyclic cyclohexanones (31 examples). In the first family of annulations, β-unsubstituted acrylates tethered to a divinyl ketone undergo cycloisomerization, providing hexahydroindenes and tetralins. In the second, partially untethered substrates undergo an intermolecular (5+1) annulation involving dimerization followed by cycloisomerization. While enantioselectivity was not possible with the former, the latter proved viable, allowing cyclohexanones to be produced with high levels of enantiopurity (most >95:5 e.r.) and exclusive diastereoselectivity (>20:1 d.r.). Derivatizations and mechanistic studies are also reported.
- Nguyen, Xuan B.,Nakano, Yuji,Duggan, Nisharnthi M.,Scott, Lydia,Breugst, Martin,Lupton, David W.
-
supporting information
p. 11483 - 11490
(2019/07/18)
-
- Photoredox-Catalyzed Cyclopropanation of 1,1-Disubstituted Alkenes via Radical-Polar Crossover Process
-
The photoredox-neutral catalyzed cyclopropanation of 1,1-disubstituted alkenes via radical addition-anionic cyclization cascade has been successfully developed. Another new protocol based on photocatalytic allylation and cyclopropanation cascade was also described between allylic halide and halomethyl radical. In addition to the successful use of bis-catecholato silicates as the alkyl radical precursors, the acyl and alkyl radicals derived from 1,4-dihydropyridines were also engaged in this radical-polar crossover process. The competing experiments displayed that the 3-exo-tet mode of cyclization preferred over 4-exo and 5-exo cyclization modes, allowing for the selective 3-exo-tet cyclization. The superior nucleofuge character of bromide over chloride and tosylate has been demonstrated in the reaction of bromomethyl radical with homoallylic (pseudo)halides. This new protocol is characterized by its redox-neutral process, broad substrate scope, mild conditions, and good functional-group compatibility. (Figure presented.).
- Luo, Wenping,Yang, Yi,Fang, Yewen,Zhang, Xinxin,Jin, Xiaoping,Zhao, Guicai,Zhang, Li,Li, Yan,Zhou, Wanli,Xia, Tingting,Chen, Bin
-
supporting information
p. 4215 - 4221
(2019/08/16)
-
- Intermolecular Aminoallylation of Alkenes Using Allyl-Oxyphthalimide Derivatives: A Case Study in Radical Polarity Effects
-
A case study on the polarity effects of radical mediated intermolecular alkene aminoallylation is presented herein. This radical group transfer method pairs vinyl ethers with electronically deficient allyl-oxyphthalimide derivatives to give difunctionalized products while illustrating the guiding effects of polarity on this radical reactivity.
- Lardy, Samuel W.,Schmidt, Valerie A.
-
supporting information
p. 6796 - 6799
(2019/11/03)
-
- BENZIMIDAZOLONE DERIVED INHIBITORS OF BCL6
-
The present invention relates to compounds of Formula I that function as inhibitors of BCL6 (B-cell lymphoma 6) activity: wherein X1, X2, R1, R2 and R3 are each as defined herein. The present invention also relates to processes for the preparation of these compounds, to pharmaceutical compositions comprising them, and to their use in the treatment of proliferative disorders, such as cancer, as well as other diseases or conditions in which BCL6 activity is implicated.
- -
-
Paragraph 00400
(2018/12/13)
-
- Preparation method of 5,5-dimethyl-3-methylene pyrrolidine-2-ketone
-
The invention discloses a preparation method of 5,5-dimethyl-3-methylene pyrrolidine-2-ketone. The preparation method comprises the following steps: (S1) under the action of strong organic alkali, formaldehyde and a compound I generate condensation reaction to obtain a compound II; (S2) the compound II and a halogenating reagent generate halogenating reaction to obtain a compound III; (S3) under the action of the strong organic alkali, the compound III and 2-nitropropane generate substitution reaction to obtain a nitryl-containing compound IV; (S4) the compound IV carries out domino reaction of reducing nitryl and closing rings under the action of a catalyst and a reducing agent to obtain the 5,5-dimethyl-3-methylene pyrrolidine-2-ketone. The preparation method disclosed by the invention has the beneficial effects that the synthetic steps are fewer, the implementation is simple and easy, no harsh reaction condition is needed, the process route is novel, the yield is more than 50%, andthe reaction heat and gas generation is well controlled. The preparation method disclosed by the invention has the characteristics of novel process route, relatively mild reaction conditions, easy expansion, large-scale production and the like.
- -
-
Paragraph 0021
(2018/04/28)
-
- 1-azaspirocycle compound, and preparation method and applications thereof
-
The invention discloses a 1-azaspirocycle compound, and preparation method and applications thereof, and belongs to the field of pharmaceutical chemistry. The 1-azaspirocycle compound with a structurerepresented by formula I, or a pharmaceutically acceptable salt or a stereisomer or a solvate or a prodrug thereof is capable of realzing combination with Autotaxin, can be taken as an Autotaxin inhibitor, and can be used for prevention and treatment of diseases with Autotaxin expression increasing pathological characteristics such as cancer and fibrosis diseases especially pulmonary fibrosis andhepatic fibrosis, metabolic diseases, myelodysplastic syndrome, cardiovascular diseases, autoimmune diseases, inflammation, neurological diseasses, or pain. Compared with single component inhibitors,the 1-azaspirocycle compound and the derivatives possesses following advantages: blocking and interfacing at the upsteam of a plurality of key signal channels are realized, tumor cell growth and transfer are relieved or dalyed, early caused drug resistance is avoided, and novel means are provided for treatment of tumor cells.
- -
-
Paragraph 0262; 0263; 0266; 0267
(2018/09/14)
-
- Polymerizable polar compound, liquid crystal composition, and liquid crystal display element
-
Provided is a polar compound having high chemical stability, high ability to align liquid crystal molecules, and high solubility in a liquid crystal composition, and which has a large voltage holding ratio when used in a liquid crystal display element. A
- -
-
Paragraph 0443; 0444; 0453; 0455; 0456
(2017/09/08)
-
- Dental composition
-
An aqueous dental glass ionomer composition comprising (a) a reactive particulate glass, (b) a linear or branched polymer comprising acidic groups, which is reactive with the particulate glass in a cement reaction, whereby the linear or branched polymer comprising acidic groups has a polymer backbone and optionally pendant groups, (c) optionally dispersed nanoparticles comprising grafted linear or branched polymer chains comprising acidic groups, and having a polymer backbone characterized in that a polymer backbone of the linear or branched polymer of component (b) and/or, if present, the grafted Sinear or branched polymer chains of component (c) are obtainable a process comprising (i) cyclopolymerizing or cyclocopolymerizing one or more compounds of the following formula (I).
- -
-
Page/Page column 20; 21
(2017/07/14)
-
- NEW PROCESSES AND INTERMEDIATES USEFUL IN SYNTHESIS OF NEP INHIBITORS
-
The invention relates to a novel process, novel process steps and novel intermediates useful in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors such as sacubitril, and prodrugs thereof.
- -
-
Page/Page column 43
(2017/04/11)
-
- Donor–Acceptor Complex Enables Alkoxyl Radical Generation for Metal-Free C(sp3)–C(sp3) Cleavage and Allylation/Alkenylation
-
The alkoxyl radical is an essential and prevalent reactive intermediate for chemical and biological studies. Here we report the first donor–acceptor complex-enabled alkoxyl radical generation under metal-free reaction conditions induced by visible light. Hantzsch ester forms the key donor–acceptor complex with N-alkoxyl derivatives, which is elucidated by a series of spectrometry and mechanistic experiments. Selective C(sp3)-C(sp3) bond cleavage and allylation/alkenylation is demonstrated for the first time using this photocatalyst-free approach with linear primary, secondary, and tertiary alkoxyl radicals.
- Zhang, Jing,Li, Yang,Xu, Ruoyu,Chen, Yiyun
-
supporting information
p. 12619 - 12623
(2017/09/11)
-
- Generation of Alkoxyl Radicals by Photoredox Catalysis Enables Selective C(sp3)-H Functionalization under Mild Reaction Conditions
-
Reported herein is the first visible-light-induced formation of alkoxyl radicals from N-alkoxyphthalimides, and the Hantzsch ester as the reductant is crucial for the reaction. The selective hydrogen atom abstraction by the alkoxyl radical enables C(sp3)-H allylation and alkenylation reactions under mild reaction conditions at room temperature. Broad substrate variations, including a structurally complexed steroid, undergo the C(sp3)-H functionalization reaction effectively with high regio- and chemoselectivity.
- Zhang, Jing,Li, Yang,Zhang, Fuyuan,Hu, Chenchen,Chen, Yiyun
-
supporting information
p. 1872 - 1875
(2016/02/03)
-
- ALKYL ALPHA-HYDROXYMETHYL ACRYLATES AS REACTIVE SURFACTANTS IN EMULSION POLYMERIZATION
-
Polymers including α-hydroxymethylacrylate units and methods of preparing polymers from α-hydroxymethylacrylates are provided. Advantageously, α-hydroxymethylacrylates may be used in an emulsion polymerization and function as a polymerizable surfactant. The ability of the α-hydroxymethylacrylates to be used as a polymerizable surfactant allows for emulsion polymerization systems to be prepared without other surfactants.
- -
-
Paragraph 0068
(2016/04/20)
-
- Probing the mechanism of allylic substitution of morita-baylis- Hillman acetates (MBHAS) by using the silyl phosphonite paradigm: Scope and applications of a versatile transformation
-
A P-C bond-forming reaction between silyl phosphonites and Morita-Baylis-Hillman acetates (MBHAs) is explored as a general alternative towards medicinally relevant ?2;-carboxyphosphinic structural motifs. Conversion rates of diversely substituted MBHAs to phosphinic acids 9 or 14that were recorded by using 31P NMR spectroscopy revealed unexpected reactivity differences between ester and nitrile derivatives. These kinetic profiles and DFT calculations support a mechanistic scenario in which observed differences can be explained from the "lateness" of transition states. In addition, we provide experimental evidence suggesting that enolates due to initial P-Michael addition are not formed. Based on the proposed mechanistic scenario in conjunction with DFT calculations, an interpretation of the E/Z stereoselectivity differences between ester and nitriles is proposed. Synthetic opportunities stemming from this transformation are presented, which deal with the preparation of several synthetically capricious phosphinic building blocks, whose access through the classical P-Michael synthetic route is not straightforward.
- Kalyva, Maria,Zografos, Alexandros L.,Kapourani, Era,Giambazolias, Evaggelos,Devel, Laurent,Papakyriakou, Athanasios,Dive, Vincent,Lazarou, Yannis G.,Georgiadis, Dimitris
-
supporting information
p. 3278 - 3289
(2015/03/05)
-
- DENTAL COMPOSITION
-
A dental cement hardened by a cement reaction involving the specific polymerizable polyacidic polymer and optionally additional crosslinkable groups, has reduced shrinkage and improved mechanical properties, in particular with regard to flexural strength and fracture toughness. Moreover, the specific polymerizable polyacidic polymer of the present invention contains a high number of acidic groups which is not reduced by the presence of polymerizable moieties, whereby water solubility of the uncured polymer is not impaired by the presence of the polymerizable moieties.
- -
-
Paragraph 0129
(2015/09/23)
-
- Synthesis of Denosomin-Vitamin D3 Hybrids and Evaluation of Their Anti-Alzheimer's Disease Activities
-
As an extension of previously conducted studies on developing an anti-Alzheimer's disease agent, denosomin (1-deoxy-24-norsominone, an artificial inducer of neurite elongation), derivatives were designed and synthesized based on the hypothesis that our denosomin would exhibit axonal extension activity via a 1,25D3-membrane-associated, rapid response steroid-binding protein (1,25D3-MARRS) pathway. The biological assay revealed that the hybridization of characteristic δ-lactone in denosomin and the triene moiety in VD3 was effective to enhance the nerve re-extension activity in amyloid β (Aβ)-damaged neurons.
- Sugimoto, Kenji,Yajima, Hisanari,Hayashi, Yusuke,Minato, Daishiro,Terasaki, Sayuri,Tohda, Chihiro,Matsuya, Yuji
-
supporting information
p. 5910 - 5913
(2015/12/11)
-
- Total synthesis of Clavilactone B: A radical cyclization-fragmentation strategy
-
A new synthetic route to clavilactone B, a naturally occurring inhibitor of epidermal growth factor receptor (EGFR) tyrosine kinase, is disclosed. The route features a sequential samarium-mediated radical cyclization-fragmentation of an indanone derivativ
- Suizu, Hiroshi,Shigeoka, Daisuke,Aoyama, Hiroshi,Yoshimitsu, Takehiko
-
supporting information
p. 126 - 129
(2017/01/17)
-
- C-H Bond Functionalization with the Formation of a C-C Bond: A Free Radical Condensation Reaction Based on the Phthalimido-N-oxyl Radical
-
The development of a new chemical process that effects the conversion RH + C=C-C-X → R-C-C=C + HX, in which X is the phthalimido-N-oxyl radical (PINO·), is reported. The reaction yields are high, mass balances are excellent, and C-H bond functionalization and C-C bond formation are achieved in a single transformation. The byproduct of the reaction, N-hydroxyphthalimide, precipitates from solution and can be easily removed by simple filtration (and recycled). The kinetic chain lengths are shorter and the reaction times are longer (relative to those of the analogous reactions of allyl bromides), most likely because PINO· is a less-reactive hydrogen-atom abstractor. There appears to be no significant difference in efficiency in the addition-elimination steps. Competition experiments reveal that Br· and PINO· are comparable in leaving group ability.
- Patil, Shradha,Chen, Liang,Tanko, James M.
-
supporting information
p. 502 - 505
(2015/10/05)
-
- Baylis-Hillman reaction as a versatile platform for the synthesis of diverse functionalized polymers by chain and step polymerization
-
The Baylis-Hillman reaction, which is a carbon-carbon bond forming reaction between an aldehyde and an activated alkene, was utilized to prepare densely functionalized monomers suitable for chain and step polymerization. By reacting formaldehyde with vari
- Peng, Chao,Joy, Abraham
-
p. 1258 - 1268
(2014/03/21)
-
- Enantioselective desymmetrization of prochiral 1,3-dinitropropanes via organocatalytic allylic alkylation
-
An enantioselective desymmetrization of prochiral 1,3-dinitropropanes has been developed which proceeds via enantiogroup differentiating organocatalytic allylic alkylation. Densely functionalized products with two vicinal stereocenters were obtained gener
- Singha Roy, Soumya Jyoti,Mukherjee, Santanu
-
supporting information
p. 121 - 123
(2014/01/06)
-
- Synthesis of enantiopure β2-homoalanine derivatives via rhodium catalyzed asymmetric hydrogenation
-
The stereoselective synthesis of chiral β2-homoalanine derivatives with 99% ee by the Rh-catalyzed enantioselective hydrogenation of prochiral 2-aminomethyl acrylates is described. The subsequent transformation to chiral 3-amino-2-methylpropanols is also demonstrated.
- Luehr, Susan,Holz, Jens,Zayas, Odalys,Seidelmann, Oliver,Domke, Lutz,Boerner, Armin
-
p. 395 - 401
(2013/06/27)
-
- A tandem 1,3-H-shift-6π-electrocyclization-cyclic 2-amido-diene intramolecular Diels-Alder cycloaddition approach to BCD-ring of atropurpuran
-
An approach toward the BCD-ring of atropurpuran via a sequence of allenic 1,3-H shift, 6π-electron pericyclic ring closure, and intramolecular Diels-Alder cycloaddition of cyclic 2-amidodiene is described.
- Hayashi, Ryuji,Ma, Zhi-Xiong,Hsung, Richard P.
-
supporting information; scheme or table
p. 252 - 255
(2012/03/08)
-
- Phosphine-catalyzed cascade [3 + 2] cyclization-allylic alkylation, [2 + 2 + 1] annulation, and [3 + 2] cyclization reactions between allylic carbonates and enones
-
The phosphine-catalyzed annulations between Morita-Baylis-Hillman adduct carbonates and enones are reported. Under the catalysis of PBu3 (20 mol %), cascade [3 + 2] cyclization-allylic alkylation, [2 + 2 + 1] annulation, and [3 + 2] cyclization reactions chemoselectively occur depending on the substituent variation of both the carbonate and enone. These reactions provide efficient syntheses of highly functionalized cyclopentenes and cyclopentanes.
- Zhou, Rong,Wang, Jianfang,Song, Haibin,He, Zhengjie
-
supporting information; scheme or table
p. 580 - 583
(2011/04/23)
-
- Scale-up of a chemo-biocatalytic route to (2 R,4 R)- and (2 S,4 S)-monatin
-
Monatin, a natural sweetener, refers to a collection of four isomers of 2-((1H-indol-3-yl)methyl)-4-amino-2-hydroxypentanedioic acid. A chemo-biocatalytic approach to kilogram quantities of enantiopure 2S,4S-monatin and 2R,4R-monatin from indole is described. Key steps in the process include a (2 + 3) cycloaddition reaction followed by nickel-catalysed reduction to construct the monatin backbone, and a highly selective enzyme resolution of the 2S,4S- and 2R,4R-monatin diastereomeric pair to afford each enantiomer in 99% ee.
- Rousseau, Amanda L.,Buddoo, Subash R.,Gordon, Gregory E. R.,Beemadu, Sharon,Kupi, B. Godfrey,Lepuru, M. Jerry,Maumela, Munaka C.,Parsoo, Arvesh,Sibiya, Duncan M.,Brady, Dean
-
experimental part
p. 249 - 257
(2011/10/02)
-
- Asymmetric synthesis of 2-alkyl-3-phosphonopropanoic acid derivatives via Rh-catalyzed asymmetric hydrogenation
-
The commercially available ferrocene-based diphosphine ligand (S c,SFc)-TaniaPhos was found to be highly effective in the Rh-catalyzed asymmetric hydrogenation of 3-aryl-2-(phosphonomethyl)propenates. Excellent enantioselectivity (90
- Luo, Li-Bin,Wang, Dao-Yong,Zhou, Xiao-Mao,Zheng, Zhuo,Hu, Xiang-Ping
-
experimental part
p. 2117 - 2123
(2012/03/27)
-
- UNIVERSAL DENTAL ADHESION-PROMOTER COMPOSITION
-
The invention relates to an adhesion-promoter composition for the adhesive joining of metallic or ceramic dental materials to radically curing dental materials, wherein the adhesion-promoter composition contains an alkoxysilane monomer (i), a phosphoric acid ester monomer (ii), a sulphur-containing monomer (iii) and an organic solvent (iv).
- -
-
-
- Enantioselective synthesis of (S)-4-methyleneglutamic acid via tandem conjugate addition-elimination under phase-transfer catalytic conditions
-
An efficient enantioselective synthetic method for (S)-4-methyleneglutamic acid is reported. Phase-transfer catalytic conjugate addition-elimination of the benzophenone imine of glycine tert-butyl ester in the presence of chiral Cinchona-derived catalysts
- Kang, Sukhoon,Shi, Qinghua,Ha, Min Woo,Ku, Jin-Mo,Cheng, Maosheng,Jeong, Byeong-Seon,Park, Hyeung-geun,Jew, Sang-sup
-
scheme or table
p. 4326 - 4329
(2010/07/09)
-
- Asymmetric total synthesis of pyranicin
-
The asymmetric total synthesis of pyranicin (1) is reported. The butenolide ring was constructed via an asymmetric alkylation/ring-closing metathesis strategy. The three stereocenters in the left-hand tetrahydropyran ring were installed by sequential chir
- Crimmins, Michael T.,Jacobs, Danielle L.
-
supporting information; experimental part
p. 2695 - 2698
(2009/10/10)
-
- Total synthesis of horsfiline: A palladium-catalyzed domino Heck-cyanation strategy
-
A total synthesis of horsfiline has been accomplished featuring a key intramolecular palladium-catalyzed domino Heck-cyanation sequence for the formation of the 3,3′-disubstituted oxindole. Georg Thieme Verlag Stuttgart.
- Jaegli, Stephanie,Vors, Jean-Pierre,Neuville, Luc,Zhu, Jieping
-
scheme or table
p. 2997 - 2999
(2010/03/03)
-
- Facile 1,3-diaza-Claisen rearrangements of tertiary allylic amines bearing an electron-deficient alkene
-
(Chemical Equation Presented) Tertiary allylic amines with an electron-deficient alkene react with isocyanates and isothiocyanates to give highly substituted ureas and thioureas arising from formal 1,3-diaza-Claisen rearrangements. Isocyanates and isothiocyanates with strong electron-withdrawing groups are more reactive. Similarly, the data suggest that a stronger electron-withdrawing substituent on the alkene favors a faster reaction, but this may be offset by sterlcs in the cyclic transition state.
- Aranha, Rachel M.,Bowser, Amy M.,Madalengoitia, Jose S.
-
supporting information; experimental part
p. 575 - 578
(2009/07/18)
-
- Synthesis of AE and BE ming analogues of the alkaloid methyllycaconitine
-
The synthesis of AE and BE analogues of the alkaloid methyllycaconitine is reported. The analogues contain two key pharmacophores: a 2-(2-methylmaleimido) benzoate ester and a homocholine motif formed from a tertiary N-(3-phenylpropyl)amine incorporated i
- Guthmann, Holger,Conole, Daniel,Wrlght, Emma,Koerber, Karsten,Barker, David,Brimble, Margaret A.
-
experimental part
p. 1944 - 1960
(2009/09/06)
-
- PRODUCTION OF MONATIN ENANTIOMERS
-
Methods for the preparation of the high intensity sweetener, monatin, 3-(1-amino-1,3-dicarboxy-3-hydroxy-but-4-yl)indole, its salts and internal condensation products thereof, including methods applicable to the large-scale production of monatin are described.
- -
-
Page/Page column 7; sheet 1
(2009/04/24)
-
- Domino palladium-catalyzed heck-intermolecular direct arylation reactions
-
A domino palladium-catalyzed Heck-intermolecular direct arylation reaction has been developed, giving access to a variety of dihydrobenzofurans, indolines, and oxindoles. A variety of sulfur-containing heterocycles such as thiazoles, thiophenes, and benzo
- Rene, Olivier,Lapointe, David,Fagnou, Keith
-
supporting information; experimental part
p. 4560 - 4563
(2009/12/05)
-
- Radiochemical 18F-fluoroarylation of unsaturated α-, β- and γ-amino acids, application to a radiolabelled analogue of baclofen
-
Unsaturated α-, β- and γ-amino acids have been investigated as substrates for the reductive Meerwein arylation. Radical reactions of this type have been shown to be a valuable tool for the fast and efficient introduction of the 4-[18F]fluorophenyl group into precursor molecules allowing short-time syntheses of potential PET radiotracers, which would be more difficult to access by other methods.
- H?fling, Sarah B.,Hultsch, Christina,Wester, Hans-Jürgen,Heinrich, Markus R.
-
experimental part
p. 11846 - 11851
(2009/04/06)
-