- Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques
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This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition-fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well-defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (Mn) of 10,000-20,000 g/mol were used to fabricate well-defined, radical-bearing polymer films by inkjet- printing.
- Janoschka, Tobias,Teichler, Anke,Krieg, Andreas,Hager, Martin D.,Schubert, Ulrich S.
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Read Online
- Design and regioselective synthesis of (2-Bromo-2-alkoxycarbonyl)ethyl acrylates as inimers for hyperbranched (Co)polyacrylates
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A route based on deaminohalogenation of serine is established to synthesize bromoinimers that can be homopolymerized to produce hyperbranched polyacrylates that are true architectural analogues of linear polyacrylates; that is, an ester group is attached to every other carbon along the polymer backbone, and each repeat unit contains a free ester side chain. Georg Thieme Verlag Stuttgart.
- Pugh, Coleen,Raveendra, Bindu,Singh, Anirudha,Samuel, Reichel,Garcia, Guillermina
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Read Online
- Suppression of chain transfer in catalytic acrylate polymerization via rapid and selective secondary insertion
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In catalytic copolymerization, undesired chain transfer after incorporation of a polar vinyl monomer is a fundamental problem. We show an approach to overcome this problem by a fast consecutive insertion. The second double bond of acrylic anhydride rapidly inserts intramolecularly to regio- and stereoselectively form a cyclic repeat unit and a primary alkyl favorable for chain growth (>96%). This results in significantly enhanced copolymer molecular weights vs monofunctional acrylate monomers.
- Jian, Zhongbao,Baier, Moritz C.,Mecking, Stefan
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Read Online
- An efficient synthesis of chiral isoquinuclidines by Diels - Alder reaction using Lewis acid catalyst
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The Diels-Alder reaction of 1,2-dihydropyridine derivatives (1-phenoxycarbonyl-1,2-dihydropyridine 1 or 1-methoxycarbonyl-1,2- dihydropyridine 4) with N-acryloyl (1S)-2,10-camphorsultam (1S)-2 {or N-acryloyl (1R)-2,10-camphorsultam (1R)-2} in the presence of Lewis acid, such as titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride afforded the endo-cycloaddition product, 2-azabicyclo[2.2.2]octane derivatives in good yields with excellent diastereoselectivity. The absolute stereochemistry assignment of the endo-cycloaddition product (1S)-5a starting from N-acryloyl (1S)-2,10-camphorsultam (1S)-2 has been established to be (1S,4R,7S) and the reaction mechanism was proposed.
- Hirama, Masafumi,Kato, Yuji,Seki, Chigusa,Nakano, Hiroto,Takeshita, Mitsuhiro,Oshikiri, Noriko,Iyoda, Masahiko,Matsuyama, Haruo
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Read Online
- Synthesis and structural characterization of a monocarboxylic inhibitor for GRB2 SH2 domain
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A monocarboxylic inhibitor was designed and synthesized to disrupt the protein–protein interaction (PPI) between GRB2 and phosphotyrosine-containing proteins. Biochemical characterizations show compound 7 binds with the Src homology 2 (SH2) domain of GRB2 and is more potent than EGFR1068 phosphopeptide 14-mer. X-ray crystallographic studies demonstrate compound 7 occupies the GRB2 binding site for phosphotyrosine-containing sequences and reveal key structural features for GRB2–inhibitor binding. This compound with a –1 formal charge offers a new direction for structural optimization to generate cell-permeable inhibitors for this key protein target of the aberrant Ras-MAPK signaling cascade.
- Haura, Eric B.,Ji, Haitao,Li, Zilu,Schonbrunn, Ernst,Sun, Luxin,Xiao, Tao,Zhang, Min
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supporting information
(2021/09/14)
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- Automated Assembly of Starch and Glycogen Polysaccharides
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Polysaccharides are Nature's most abundant biomaterials essential for plant cell wall construction and energy storage. Seemingly minor structural differences result in entirely different functions: cellulose, a β (1-4) linked glucose polymer, forms fibrils that can support large trees, while amylose, an α (1-4) linked glucose polymer forms soft hollow fibers used for energy storage. A detailed understanding of polysaccharide structures requires pure materials that cannot be isolated from natural sources. Automated Glycan Assembly provides quick access to trans-linked glycans analogues of cellulose, but the stereoselective installation of multiple cis-glycosidic linkages present in amylose has not been possible to date. Here, we identify thioglycoside building blocks with different protecting group patterns that, in concert with temperature and solvent control, achieve excellent stereoselectivity during the synthesis of linear and branched α-glucan polymers with up to 20 cis-glycosidic linkages. The molecules prepared with the new method will serve as probes to understand the biosynthesis and the structure of α-glucans.
- Delbianco, Martina,Seeberger, Peter H.,Zhu, Yuntao
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supporting information
p. 9758 - 9768
(2021/06/30)
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- Multicatalytic Transformation of (Meth)acrylic Acids: a One-Pot Approach to Biobased Poly(meth)acrylates
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Shifting from petrochemical feedstocks to renewable resources can address some of the environmental issues associated with petrochemical extraction and make plastics production sustainable. Therefore, there is a growing interest in selective methods for transforming abundant renewable feedstocks into monomers suitable for polymer production. Reported herein are one-pot catalytic systems, that are active, productive, and selective under mild conditions for the synthesis of copolymers from renewable materials. Each system allows for anhydride formation, alcohol acylation and/or acid esterification, as well as polymerization of the formed (meth)acrylates, providing direct access to a new library of unique poly(meth)acrylates.
- Fouilloux, Hugo,Placet, Vincent,Qiang, Wei,Robert, Carine,Thomas, Christophe M.
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supporting information
p. 19374 - 19382
(2021/07/21)
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- METHOD FOR PRODUCING (METH)ACRYLIC ACID ANHYDRIDE
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PROBLEM TO BE SOLVED: To provide an industrially useful method for producing a (meth)acrylic acid anhydride capable of producing a (meth)acrylic acid anhydride with high yield and high purity. SOLUTION: There is provided a method for producing a (meth)acrylic acid anhydride by reacting a (meth)acrylic acid alkali metal salt and sulfonyl chloride in an organic solvent. The (meth)acrylic acid alkali metal salt includes lithium (meth)acrylate, sodium (meth)acrylate, potassium (meth)acrylate or the like. Among these (meth)acrylic acid alkali metal salts, preferable are sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate in consideration of market feedability, reactivity and easiness of treatment after the reaction. In addition, the sulfonyl chloride includes benzenesulfonyl chloride, p-toluenesulfonyl chloride and methanesulfonyl chloride. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0024-0031; 0040
(2021/05/28)
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- METHOD FOR PRODUCING N-BENZYL-2-BROMO-3-METHOXYPROPIONAMIDE AND INTERMEDIATES THEREOF
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The present invention provides an industrially-preferable method for safely producing N-benzyl-2-bromo-3-methoxypropionamide at a high yield but at low cost. The method for producing of the present invention includes: in sequence, an amidation process that causes diacrylic anhydride to react with benzylamine in a solvent to obtain N-benzylacrylamide; a bromination process that causes N-benzylacrylamide to react with bromine in a solvent to obtain N-benzyl-2,3-dibromopropionamide; and a methoxylation process that causes N-benzyl-2,3-dibromopropionamide to react with methanol in the presence of a base to obtain N-benzyl-2-bromo-3-methoxypropionamide.
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Paragraph 0107-0109; 0136
(2020/05/02)
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- METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING CARBOXYLIC ACID ESTER
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Provided is a production method whereby corresponding carboxylic acid anhydrides and carboxylic acid esters can be obtained at high yield from various carboxylic acids even without a solvent and near room temperature. A method for producing a carboxylic acid anhydride represented by formula (II), the method comprising reacting a compound represented by formula (I) and a carboxylic acid in the presence of a Group II metal compound having an ionic ligand containing an oxygen atom. A method for producing a carboxylic acid ester, the method comprising reacting a carboxylic acid anhydride produced by the aforementioned method and an alcohol. In formula (I), R1 represents a C1-20 hydrocarbon group. In formula (II), R2 represents a C1-20 hydrocarbon group.
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Paragraph 0075; 0076
(2017/04/18)
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- Synthesis of (meth)acrylic anhydride by transanhydrization
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The present invention relates to a process for preparing an anhydride of formula A-C(═O)—O—(O═)C-A, where A is —CR═CH2 and R is —H or —CH3, comprising: a) a step of reacting an anhydride B—C(═O)—O—(O═)C—B with an acid A-COOH, A being as defined above, wherein the step results in the formation of an anhydride A-C(═O)—O—(O═)C—B and of an acid B—COOH, A and B being such that said acid B—COOH is more volatile than said acid A-COOH, and b) a step of reacting said anhydride A-C(═O)—O—(O═)C—B with the acid A-COOH under conditions such that the amount of acid B—COOH is less than the amount of acid A-COOH, resulting in the formation of the anhydride A-C(═O)—O—(O═)C-A, in which said reaction steps are carried out in the presence of an acid catalyst which is more volatile than said anhydride A-C(═O)—O—(O═)C-A.
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Paragraph 0113-0122
(2016/05/19)
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- Synthesis of (meth)acrylic anhydride by transanhydrization
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The present invention relates to a process for preparing an anhydride of formula A-C(═O)—O—(O═)C-A, where A is —CR═CH2 and R is —H or —CH3, comprising: a) a step of reacting an anhydride B—C(═O)—O—(O═)C—B with an acid A-COOH, A being as defined above, wherein the step results in the formation of an anhydride A-C(═O)—O—(O═)C—B and of an acid B—COOH, A and B being such that said acid B—COOH is more volatile than said acid A-COOH, and b) a step of reacting said anhydride A-C(═O)—O—(O═)C—B with the acid A-COOH under conditions such that the amount of acid B—COOH is less than the amount of acid A-COOH, resulting in the formation of the anhydride A-C(═O)—O—(O═)C-A, in which said reaction steps are carried out in the presence of an acid catalyst which is more volatile than said anhydride A-C(═O)—O—(O═)C-A.
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Paragraph 0112-0121
(2015/07/27)
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- Discovery of a potent boronic acid derived inhibitor of the HCV RNA-dependent RNA polymerase
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A boronic acid moiety was found to be a critical pharmacophore for enhanced in vitro potency against wild-type hepatitis C replicons and known clinical polymorphic and resistant HCV mutant replicons. The synthesis, optimization, and structure-activity relationships associated with inhibition of HCV replication in a subgenomic replication system for a series of non-nucleoside boron-containing HCV RNA-dependent RNA polymerase (NS5B) inhibitors are described. A summary of the discovery of 3 (GSK5852), a molecule which entered clinical trials in subjects infected with HCV in 2011, is included.
- Maynard, Andrew,Crosby, Renae M.,Ellis, Byron,Hamatake, Robert,Hong, Zhi,Johns, Brian A.,Kahler, Kirsten M.,Koble, Cecilia,Leivers, Anna,Leivers, Martin R.,Mathis, Amanda,Peat, Andrew J.,Pouliot, Jeffrey J.,Roberts, Christopher D.,Samano, Vicente,Schmidt, Rachel M.,Smith, Gary K.,Spaltenstein, Andrew,Stewart, Eugene L.,Thommes, Pia,Turner, Elizabeth M.,Voitenleitner, Christian,Walker, Jill T.,Waitt, Greg,Weatherhead, Jason,Weaver, Kurt,Williams, Shawn,Wright, Lois,Xiong, Zhiping Z.,Haigh, David,Shotwell, J. Brad
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p. 1902 - 1913
(2014/04/03)
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- Synthesis of inimers and hyperbranched polymers
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An inimer, and process for making same, having the following formula: wherein X=halogen, nitroxide, thioester; R═H or CH3; and R′=aliphatic, non-aliphatic, linear or branched, mesogenic, non mesogenic, chiral, achiral, hydrocarbon, non-hydrocarbon, selected from fluorocarbon, oligo(oxyethylene) and siloxane substituents, alkyl, aryl, mesogenic group, non-mesogenic group, aliphatic, non-aliphatic, siloxane, perfluoroalkyl, perfluoroaryl, or other fluorocarbon group, and polymers, and the process of making them, from the inimer.
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Page/Page column 18-19
(2013/09/12)
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- Synthesis of unsaturated diesters of primary, secondary and tertiary diols derived from dimethyl (+)-tartrate and galactaric acid
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The preparation of symmetrical unsaturated diesters of dioe first was the reaction of mixed anhydrides, obtained from α,β-unsaturated acids and benzoyl chloride, with diols 3 (primary), 5 (secondary), and 7 (primary), i.e., Yamaguchi-SantaLucia's method, however only the symmetrical diacrylates of diols 5 and 7 were obtained quantitatively. In the other ten cases studied the reactions led to mixtures of symmetrical and unsymmetrical diesters that were difficult to separate. The mixed anhydrides did not react with the tertiary diols 4 (TADDOL) and 8. The average yield obtained in desired symmetrical diesters in the 12 cases studied was 54 %. The acylation of the diols with the anhydrides of the unsaturated acids, was found to be an excellent method, leading to the symmetrical unsaturated diesters of diols 3, 5, 7 as the only products of reaction, in an average yield of 83 %. Unfortunately, the method could not be applied to diesters derived from the tertiary diols 4 (TADDOL) and 8. The third method studied was the reaction between the alkoxides prepared with solutions of nBuLi in ether with the unsaturated acid chlorides at-50 °C, i.e., the Kaiser-Woodruff protocol. This was found to be the best of the three methods tested. The method was applied with success to the synthesis of the desired unsaturated diesters derived from diols 3-5, 7, and 8. The average yield of the 19 cases studied was 78 %. Copyright
- Scoccia, Jimena,Gerbino, Dario C.,Terraza, Victor F.,Zuniga, Adriana E.,Podesta, Julio C.
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p. 4418 - 4426
(2013/07/26)
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- Asymmetric synthesis of isoquinuclidines by Diels-Alder reaction of 1,2-dihydropyridine utilizing a chiral Lewis acid catalyst
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The chiral isoquinuclidine derivative, 2-azabicyclo[2.2.2]octane ring system, endo-(7R)-3 was obtained in good yield with excellent diastereoselectivity (up to 92% de) by Diels-Alder reaction of 1-(phenoxycarbonyl)-1,2-dihydropyridine 1 with N-acryloyl-(4S)-4- benzyloxazolidin-2-one (4S)-2 using titanium-(2R,3R)-TADDOLate 4 as a chiral Lewis acid catalyst in toluene at 0 °C. On the other hand, endo-(7S)-3 was obtained in good yield with excellent diastereoselectivity (up to 97% de) by Diels-Alder reaction of 1 with (4R)-2 using Cu(OTf)2/(4S,4′S)- bis(oxazoline) catalyst 8 as a chiral Lewis acid catalyst in dichloromethane at 0 °C. In these reactions, the choice of solvent and the combination of titanium-(2R,3R)-TADDOLate 4 {or Cu(II)/(4S,4′S)-bis(oxazoline) 8} and dienophile (4S)-2 {or (4R)-2} are very important. The stereochemistry of endo-(7R)-3 has been established to be (1R,4S,7R) and the reaction mechanism is proposed.
- Seki, Chigusa,Hirama, Masafumi,Hutabarat, N.D.M. Romauli,Takada, Junko,Suttibut, Chonticha,Takahashi, Hideto,Takaguchi, Takuya,Kohari, Yoshihito,Nakano, Hiroto,Uwai, Koji,Takano, Nobuhiro,Yasui, Mitsukuni,Okuyama, Yuko,Takeshita, Mitsuhiro,Matsuyama, Haruo
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experimental part
p. 1774 - 1781
(2012/03/10)
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- Highly enantioselective synthesis of isoquinuclidine by diels-alder reaction of 1,2-dihydropyridine utilizing chiral bisoxazoline-Cu(II) complex
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The enantioselective Diels-Alder (D-A) reaction between N-phenoxycarbonyl- or N-benzyloxycarbonyl-1,2-dihydropyridine (1a or 1b) and N(2)-acryloyl-N(1)-(1- naphthylmethyl)-5,5-dimethylpyrazolidin-3-one (2b) using (S,S)-bisoxazoline- Cu(II) catalyst (A, B, C or D) has been investigated. Utilizing (S,S)-t-Bu-bisoxazoline-Cu(II) catalyst C, the D-A reaction of 1a and 2 afforded the endo-(7S)-isoquinuclidines (3, 4 or 5) in good chemical yields with high enantioselectivity (up to 99% e.e.).
- Hutabarat, N.D.M. Romauli,Seki, Chigusa,Shimizu, Takashi,Hirama, Masafumi,Kohari, Yoshihito,Nakano, Hiroto,Uwai, Koji,Takano, Nobuhiro,Kwon, Eunsang,Matsuyama, Haruo
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p. 203 - 217
(2013/08/23)
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- SYNTHESIS OF INIMERS AND HYPERBRANCHED POLYMERS
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An inimer, and process for making same, having the following formula: wherein X=halogen, nitroxide, thioester; R=H or CH3; and R′=aliphatic, non-aliphatic, linear or branched, mesogenic, non mesogenic, chiral, achiral, hydrocarbon, non-hydrocarbon, selected from fluorocarbon, oligo(oxyethylene) and siloxane substituents, alkyl, aryl, mesogenic group, non-mesogenic group, aliphatic, non-aliphatic, siloxane , perfluoroalkyl, perfluoroaryl, or other fluorocarbon group, and polymers, and the process of making them, from the inimer.
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- Diels-alder cycloaddition strategy for kinetic resolution of chiral pyrazolidinones
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A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid catalyst.
- Sibi, Mukund P.,Kawashima, Keisuke,Stanley, Levi M.
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supporting information; experimental part
p. 3894 - 3897
(2009/12/05)
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- Nitrile Ylides: Diastereoselective cycloadditions using chiral oxzolidinones without Lewis acid
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"Chemical Equation Presented" Lewis acid complexation Is generally required for chiral-auxiliary-controlled stereoselectivity, and chiral Lewis acid catalysis Is frequently optimal for Introducing asymmetry. In this work, we show that nitrlle ylide cycloadditions to electron-poor acceptors attached to chiral auxiliaries proceed In high yield and stereoselectivity in the absence of Lewis acids. In contrast, chiral Lewis acids are Inferior In these cycloadditions.
- Mukund P, Sibi,Soeta, Takahlro,Jasperse, Craig P.
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supporting information; experimental part
p. 5366 - 5369
(2010/02/28)
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- METHOD FOR THE PRODUCTION OF (METH)ACRYLIC ANHYDRIDE
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The present invention relates to an improved method for manufacturing (meth)acrylic anhydride by transanhydrization between (meth)acrylic acid and acetic anhydride, in the presence of air and in the presence of at least one polymerization inhibitor, characterized in that the polymerization inhibitor is chosen from the group formed from (a) metal salts of thiocarbamic or dithiocarbamic acid and their mixtures with a phenolic derivative or phenothiazine and its derivatives, and (b) N-oxyl compounds as a mixture with 2,6-di-tert-butyl-4-methylphenol taken alone or in the presence of 2,4-dimethyl-6-tert-butylphenol.
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Page/Page column 3
(2009/09/28)
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- METHOD FOR THE CONTINUOUS PRODUCTION OF UNSATURATED CARBOXYLIC ACID ANHYDRIDES
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Process for continuously preparing unsaturated carboxylic anhydrides of the general formula I [in-line-formulae]R—C(O)—O—C(O)—R??(I)[/in-line-formulae] in which R is an unsaturated organic radical having 2 to 12 carbon atoms by transanhydridization of an aliphatic carboxylic anhydride with a carboxylic acid of the general formula II [in-line-formulae]R—COOH??(II)[/in-line-formulae] in which R is as defined above in a rectification column having an upper, middle and lower region, characterized in that f) an inert boiling oil is initially charged in the bottom of the column,g) the reactants are fed into a reaction region in stoichiometric ratios,h) the carboxylic acid formed as the by-product is withdrawn at the top of the column,i) the unconverted reactants are recycled into the reaction region andj) the product of the formula I is obtained via a side draw, preferably between the middle and lower column region.
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Page/Page column 3-4
(2009/10/30)
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- METHOD FOR PURIFYING POLYMERIZABLE COMPOUNDS
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Process for distillatively purifying polymerizable compounds using a high-boiling, inert, thermally long-term-stable substance as a boiling oil, characterized in that the boiling oil is disposed in the bottom of a rectification column.
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Page/Page column 2-3
(2009/07/17)
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- Asymmetric synthesis of β2-amino acids: 2-substituted-3-aminopropanoic acids from N-acryloyl SuperQuat derivatives
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Conjugate addition of lithium dibenzylamide to (S)-N(3)-acryloyl-4- isopropyl-5,5-dimethyloxazolidin-2-one (derived from l-valine) and alkylation of the resultant lithium β-amino enolate provides, after deprotection, a range of (S)-2-alkyl-3-aminopropanoic acids in good yield and high ee. Alternatively, via a complementary pathway, conjugate addition of a range of secondary lithium amides to (S)-N(3)-(2′-alkylacryloyl)-4-isopropyl-5,5- dimethyloxazolidin-2-ones, diastereoselective protonation with 2-pyridone, and subsequent deprotection furnishes a range of (R)-2-alkyl- and (R)-2-aryl-3-aminopropanoic acids in good yield and high ee. Additionally, the boron-mediated aldol reaction of β-amino N-acyl oxazolidinones is a highly diastereoselective method for the synthesis of a range of β-amino- β′-hydroxy N-acyl oxazolidinones. The Royal Society of Chemistry.
- Beddow, James E.,Davies, Stephen G.,Ling, Kenneth B.,Roberts, Paul M.,Russell, Angela J.,Smith, Andrew D.,Thomson, James E.
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p. 2812 - 2825
(2008/03/12)
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- PIGMENT DISPERSIONS WITH POLYMERIC DISPERSANTS HAVING PENDING CHROMOPHORE GROUPS
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A pigment dispersion comprising a colour pigment and a polymeric dispersant having at least one pending chromophore group covalently bound to the polymeric backbone of the polymeric dispersant through a linking group wherein the colour pigment is selected from the group consisting of monoazo pigments, disazo pigments, β-naphtol pigments, naphtol AS pigments, azo pigment lakes, benzimidazolone pigments, disazo condensation pigments, metal complex pigments, isoindolinone pigments, isoindolinine pigments, phthalocyanine pigments, quinacridone pigments, diketopyrrolo-pyrrole pigments, thioindigo pigments, anthraquinone pigments, anthrapyrimidine pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, anthanthrone pigments, isoviolanthrone pigments, aluminium pigment lakes, dioxazine pigments, triarylcarbonium pigments and quinophthalone pigments; the at least one pending chromophore group has a molecular weight which is smaller than 85 % of the molecular weight of the colour pigment; the at least one pending chromophore group occurs as a side group on the polymeric backbone and not as a group in the polymeric backbone itself or occurring solely as an end group of the polymeric backbone; the linking group consists of all the atoms between the polymeric backbone and the first atom of the aromatic group by which the pending chromophore group is linked to the polymeric backbone; and the at least one pending chromophore group has a similarity coefficient SIM of at least 0.75, with the similarity coefficient defined by (I) wherein, M represents the number of atoms in the at least one pending chromophore group; P represents the number of atoms in the colour pigment; C represents the largest number of atoms in common between the at least one pending chromophore group and the colour pigment as one continuous structure; and t is an integer representing the number of times that the largest number of atoms in common C fits into the organic colour pigment, without using atoms of the colour pigment twice. A method for preparing the pigment dispersion wherein the polymeric dispersant is prepared by copolymerizing a monomer already containing the pending chromophore group is also disclosed.
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Page/Page column 57-58
(2010/11/25)
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- PIGMENT DISPERSIONS WITH POYMERIC DISPERSANTS HAVING PENDING CHROMOPHORE GROUPS
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A pigment dispersion comprising a colour pigment represented by formula (I) wherein, X1 to X4 are independently selected from the group consisting of hydrogen and a halogen atom, R1 to R10 are independently selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, and an ethoxy group, and a polymeric dispersant having via a linking group covalently linked to its polymeric backbone at least one pending chromophore group which has a molecular weight smaller than 90% of the molecular weight of the colour pigment, wherein the at least one pending chromophore group is a chromophore group occurring as a side group on the polymeric backbone and not a group in the polymeric backbone itself or occurring solely as an end group of the polymeric backbone, and the at least one pending chromophore group is represented by formula (II) wherein, one of L1, L2 or L3 is the linking group and is selected from the group consisting of an aliphatic group, a substituted aliphatic group, an unsaturated aliphatic group and a substituted unsaturated aliphatic group; L1, L2 and/or L3, if not representing the linking group, are independently selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, an alkoxy group, a carboxylic acid group, an ester group, an acyl group, a nitro group and a halogen; AR1 and AR2 represent an aromatic group; and n represents the integer 0 or 1. The pigment dispersion can be advantageously used in inkjet inks. Also disclosed are methods for preparing the inkjet ink.
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Page/Page column 48-50
(2010/11/25)
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- PIGMENT DISPERSIONS WITH POLYMERIC DISPERSANTS HAVING PENDING CHROMOPHORE GROUPS.
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A pigment dispersion comprising a colour pigment represented by formula (I) wherein, R1 is selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, -CF3 , -COOH, -COOCH3 and; R2, R4 and R5 are independently selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group,-CF3 , -COOH and -COOCH3; R3 is selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group,-CF3, -COOH, -COOCH3, -SO2NH-C6H5, -CONH-C6H5, -CONH-C6H5-CONH2 and -CONH2 ; R6 and R7 are independently selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group,- CF3 , -COOH and -COOCH3, or R6 and R7 represent the necessary atoms to form an imidazolone ring; and a polymeric dispersant having via a linking group covalently linked to its polymeric backbone at least one pending chromophore group which has a molecular weight smaller than 95% of the molecular weight of said colour pigment. The pigment dispersion can be advantageously used in inkjet inks.
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Page/Page column 62-63
(2010/11/25)
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- PIGMENT DISPERSIONS WITH POLYMERIC DISPERSANTS HAVING PENDING CHROMOPHORE GROUPS.
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A pigment dispersion comprising a colour pigment represented by formula (I) wherein, R1 to R10 are independently selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, - CF3 , -COOH, -COOCH3; -SO2NH-C6H5, -CONH-C6H5, -CONH-C6H5-CONH2 and -CONH2; and a polymeric dispersant having via a linking group covalently linked to its polymeric backbone at least one pending chromophore group which has a molecular weight smaller than 95% of the molecular weight of said colour pigment. The pigment dispersion can be advantageously used in inkjet inks.
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Page/Page column 45-47
(2010/11/25)
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- PIGMENT DISPERSIONS WITH POLYMERIC DISPERSANTS HAVING PENDING CHROMOPHORE GROUPS.
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A pigment dispersion comprising a colour pigment and a polymeric dispersant having at least one pending chromophore group covalently bound to the polymeric backbone of the polymeric dispersant through a linking group wherein the at least one pending chromophore group is a derivative from a colour pigment selected from the group consisting of monoazo pigments, disazo pigments, β-naphtol pigments, naphtol AS pigments, azo pigment lakes, benzimidazolone pigments, disazo condensation pigments, metal complex pigments, isoindolinone pigments, isoindolinine pigments, phthalocyanine pigments, quinacridone pigments, diketopyrrolo-pyrrole pigments, thioindigo pigments, anthraquinone pigments, anthrapyrimidine pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, anthanthrone pigments, isoviolanthrone pigments, aluminium pigment lakes, dioxazine pigments, triarylcarbonium pigments and quinophthalone pigments; the at least one pending chromophore group is a chromophore group occurring as a side group on the polymeric backbone and not a group in the polymeric backbone itself or occurring solely as an end group of the polymeric backbone; the linking group consists of all the atoms between the polymeric backbone and the first atom of the aromatic group by which the pending chromophore group is linked to the polymeric backbone; the polymeric dispersant has a polymeric backbone with a polymerization degree between 5 and 1000; and at most 30 % of the monomer units of the polymeric backbone have a pending chromophore group. The pigment dispersion can be advantageously used in inkjet inks. Also disclosed is a method for preparing the pigment dispersion comprising the step of preparing the polymeric dispersant by copolymerizing a monomer already containing the pending chromophore group.
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Page/Page column 41-42
(2010/11/25)
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- An efficient synthetic methodology of chiral isoquinuclidines by the enantioselective Diels-Alder reaction of 1,2-dihydropyridines using chiral cationic palladium-phosphinooxazolidine catalyst
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High purity chiral isoquinuclidines (97% ee) were obtained from the enantioselective Diels-Alder reaction of 1-phenoxycarbonyl-1,2-dihydropyridine with 1-benzyl-2-acryloylpyrazolidin-3-one using chiral cationic palladium-phosphinooxazolidine (Pd-POZ) catalyst. The obtained DA adduct was easily converted to the chiral piperidine derivative bearing three stereogenetic centers in the structure.
- Nakano, Hiroto,Tsugawa, Natsumi,Takahashi, Kouichi,Okuyama, Yuko,Fujita, Reiko
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p. 10879 - 10887
(2007/10/03)
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- SuperQuat 5,5-dimethyl-4-iso-propyloxazolidin-2-one as a mimic of Evans 4-tert-butyloxazolidin-2-one
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The incorporation of a gem-dimethyl group at the 5-position of a chiral oxazolidinone biases the conformation of the adjacent C(4)-stereodirecting group such that the gem-dimethyl-4-iso-propyl combination mimics a C(4)-tert-butyl group, providing higher levels of stereocontrol than a simple 4-iso-propyloxazolidinone. The generality of this principle is demonstrated with applications in stereoselective enolate alkylations, kinetic resolutions, Diels-Alder cycloadditions and Pd-catalysed asymmetric acetalisation reactions. The Royal Society of Chemistry 2006.
- Bull, Steven D.,Davies, Stephen G.,Garner, A. Christopher,Kruchinin, Dennis,Key, Min-Suk,Roberts, Paul M.,Savory, Edward D.,Smith, Andrew D.,Thomson, James E.
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p. 2945 - 2964
(2008/02/09)
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- METHOD FOR PRODUCING ACRYLOYL AZIDE
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PROBLEM TO BE SOLVED: To provide a method for easily and efficiently producing an acryloyl azide from acrylic acid which may have a substituent at an α-carbon atom or its acid anhydride, and a method for easily and efficiently producing an N-vinylisocyanate and an N-vinylcarbamate from the acryloyl azide. SOLUTION: The method for producing the acryloyl azide is to react the acrylic acid which may have a substituent on the α-carbon atom or its acid anhydride with an azide compound. The method for producing the N-vinyl carbamate is to perform a rearrangement reaction of the acryloyl azide to obtain the N-vinylisocyanate which is reacted with an alcohol.
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Page/Page column 16
(2008/06/13)
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- Chiral 2,2′-Binaphthyldiimine-Nickel(II) Complexes as Lewis Acid Catalysts for Enantioselective Diels-Alder Reactions
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The preparation and application of a novel class of chiral Lewis acid catalysts based on chiral 2,2′-binaphthyldiimine ligands are described. Among the binaphthyldiimine-metal complexes tested, N,N′ -bis(2-quinolylmethylene)-1,1′-binaphthyl-2,2′-diamine-Ni(II) complex was found to be an efficient chiral Lewis acid catalyst for asymmetric Diels-Alder reactions (endo: up to 96% ee) between cyclopentadiene and 3-alkenoyl-2-oxazolidinones. This catalyst is easy to prepare and is efficient; that is, 1 mol% of the Ni(II) catalyst promoted a Diels-Alder reaction between cyclopentadiene and 3-acryloyl-2-oxazolidinone smoothly with high enantioselectivity (endo: 90% ee).
- Suga, Hiroyuki,Kakehi, Akikazu,Mitsuda, Masashi
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p. 561 - 568
(2007/10/03)
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- PROCESS FOR PRODUCING ACID ANHYDRIDE
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According to the present invention there is provided a process for producing an acid anhydride by reacting a carboxylic acid, preferably a carboxylic acid having a polymerizable group, with a sulfonyl halide compound in the presence of a tertiary amine or in the presence of a tertiary amine and an inorganic base, wherein the tertiary amine or the tertiary amine and the inorganic base are used in an amount of 0.9 to 1.2 equivalents relative to the acid generated from the sulfonyl halide compound.
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- Experimental determination of the absolute enantioselectivity of an antibody-catalyzed Diels-Alder reaction and theoretical explorations of the origins of stereoselectivity
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The exo and endo Diels-Alder adducts of p-methoxycarbonylbenzyl trans-1,3-butadiene-1-carbamate and N,N-dimethylacrylamide have been synthesized, and the absolute configurations of resolved enantiomers have been determined. On the basis of this information, the absolute enantioselectivities of the Diels-Alder reaction catalyzed by antibodies 13G5 and 4D5 as well as other catalytic antibodies elicited in the same immunizations have been established. The effects of different arrangements of catalytic residues on the structure and energetics of the possible Diels-Alder transition states were modeled quantum mechanically at the B3LYP/6-311++G**//B3LYP/6-31+G** level of theory. Flexible docking of these enantiomeric transition states in the antibody active site followed by molecular dynamics on the resulting complexes provided a prediction of the transition -state binding modes and an explanation of the origin of the observed enantioselectivity of antibody 13G5.
- Cannizzaro, Carina E.,Ashley, Jon A.,Janda,Houk
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p. 2489 - 2506
(2007/10/03)
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- Asymmetric formation of quaternary centers through aza-annulation of chiral β-enamino amides with acrylate derivatives
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The stereoselective formation of six-membered nitrogen heterocycles that contain an asymmetric quaternary carbon center was achieved through aza- annulation of β-enamino amide substrates with activated acrylate derivatives. Condensation of a racemic β-keto amide with an optically active primary amine, either (R)-α-methylbenzylamine or α-amino esters, generated the corresponding optically active tetrasubstituted secondary enamine, in which the enamine tautomer was stabilized through conjugation with an amide carbonyl. Treatment of the intermediate enamine with acryloyl chloride, acrylic anhydride, or sodium acrylate/ethyl chloroformate resulted in aza- annulation to give the corresponding δ-lactam with high diastereoselectivity (>96% de). For the variety of different β-enamino amide substrate classes examined in this reaction, the optimum method for activation of the acrylate derivative was the use of EtO2CCl. When aza-annulation was performed with an α-acetamido-substituted acrylate derivative, the stereoselective formation of the quaternary carbon center was accompanied by poor selectivity for generation of the center α to the lactam carbonyl. Crystallographic analysis of one α-amido aza-annulation product was performed to identify the key structural features of these molecules.
- Benovsky, Petr,Stephenson, Gregory A.,Stille, John R.
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p. 2493 - 2500
(2007/10/03)
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- Method of preventing prostatic cancer development
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A series of benzoquinolin-3-ones are pharmaceuticals effective in preventing the development of prostatic cancer, or preventing or treating the metastasis to bone of prostatic cancer.
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- Process of synthesizing N-acyl auxiliaries
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A process of synthesizing N-acyl auxiliary compounds is disclosed. A compound of the formula: STR1 is reacted with an anhydride in the presence of a lithium salt and an amine base to produce the N-acylated auxiliary.
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- Methods for inhibiting bone loss
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The present invention provides methods of inhibiting bone loss in mammals via the administration to a mammal in need of such treatment an effective amount of a compound from a series of benzoquinolin-3-ones. Such compounds also are sequentially or concurrently coadministered with a bone antiresorptive agent or a bone anabolic agent.
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- Syntheis of benzoquinolinones
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A 1-pot process for preparing 10b-methyl-3-oxo-benzo[f] quinolines.
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- Process for preparation of benzo[f]quinolinones
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A series of benzoquinolin-3-ones are pharmaceuticals effective in treating conditions consequent on both Type I and Type II 5α-reductase and their preparation is disclosed.
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- Acrylate ester
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The present invention concerns a method for the production of olefin anhydrides, such as acrylic anhydride and methacrylic anhydride, via reactions between an aromatic acid chloride, such as benzoyl chloride, and carboxylate ions of the olefin acid corresponding to the anhydride to be produced. The method of the invention may be conducted without the use of a solvent, catalyst, polymerization inhibitor, or an external source of heat. Moreover the acrylic anhydrides of the invention can be used to produce high yields of acrylate esters by means of room-temperature reactions, without mineral acid catalysis.
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- Process of synthesizing n-acyl auxiliaries
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A process of synthesizing N-acyl auxiliary compounds is disclosed. A compound of the formula: STR1 is reacted with an anhydride in the presence of a lithium salt and an amine base to produce the N-acylated auxiliary.
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- Construction of Hydroxylated Alkaloids (+/-)-Mannonolactam, (+/-)-Deoxymannojirimycin, and (+/-)-Prosopinine through Aza-Annulation
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The aza-annulation of β-enamino carbonyl substrates with acrylate derivatives provides an efficient and convenient route for the regioselective construction of δ-lactams.This two-step ring-forming sequence involved initial generation of the benzyl enamine through either a condensation or conjugate addition reaction with BnNH2, followed by aza-annulation with acryloyl chloride or acrylic anhydride.Controlled by the rigid framework of the intermediate lactam, introduction of ring substituents was accomplished with high relative stereoselectivity.The carbonyl functionality, which was necessary to direct the regioselectivity of the aza-annulation reaction, was then transformed into a protected hydroxyl substituent through Baeyer-Villiger oxidation.The resultant δ-lactam product was used as a valuable intermediate in the synthesis of three natural products.Subsequent modification of this δ-lactam gave the naturally occurring α-mannosidase inhibitors (+/-)-mannonolactam and (+/-)-deoxymannojirimycin, while synthesis of the alkaloid (+/-)-prosopinine was accomplished through homologation of the lactam carbonyl.
- Cook, Gregory R.,Beholz, Lars G.,Stille, John R.
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p. 3575 - 3584
(2007/10/02)
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- Formation of 1,2,3,4-Tetrahydro-2-pyridones by Aza-Annulation of Imines with Acrylate Derivatives
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The aza-annulation of imines with activated acrylate derivatives was studied as a means of preparing the corresponding 1,2,3,4-tetrahydro-2-pyridones.Through the use of reagents known to facilitate the formation of amide bonds from carboxylic acids, several methods of activating the acrylate species were compared.The acrylate derivatives studied were acryloyl chloride and acrylic anhydride as well as acrylic acid activated by reaction with EtO2CCl, (PhO)2P(O)N3, or MCPI.Optimum annulation was obtained with imines derived from cyclohexanone to produce octahydro-2-quinolone products.The N-isobutylimine prepared from cyclopentanone also produced selective ring annulation to efficiently produce the corresponding bicyclic product, but the reaction with the imine of n-butanal produced lower yields of cyclic product.Ring formation was relatively unaffected by substituents at the α-position of the acrylate derivative, demonstrated by the use of methacrylate, but β-substituents hindered the annulation process and, in turn, increased the amounts of byproduct resulting from only N-acylation of the imine.Increasing the steric bulk of the imine alkyl substituent produced the opposite effect; the relative amount of N-acylation compared to complete aza-annulation was diminished as the size of the substituent was increased.Mechanistic features of the reaction are discussed in terms of product distribution and competition experiments.
- Paulvannan, K.,Stille, John R.
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p. 5319 - 5328
(2007/10/02)
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- PHASE MANAGED ORGANIC SYNTHESIS 3. SYMMETRICAL ANHYDRIDES FROM CARBOXYLIC ACIDS VIA POLYMER ASSISTED REACTION.
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Symmetrical anhydrides are produced quickly and in high yield by treating mixtures of a carboxylic acid and one-half equivalent thionyl chloride in dichloromethane with a solid-state copolymer of 4-vinylpyridine.This conversion is accomplished equally well in batch or column mode.
- Fife, Wilmer K.,Zhang, Zhi-dong
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p. 4937 - 4940
(2007/10/02)
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