- Selective trioxolane based bifunctional molecular linkers for covalent heme surface functionalisation
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A bifunctional molecular linker containing both aryl diazonium and trioxolane groups was synthesised and its ability to sequentially functionalise glassy carbon and covalently immobilise heme investigated. Functionalisation was demonstrated by electrochemical techniques.
- McConville,Bradley,Zhou,Schiffrin,O'Neil
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- Bromination of adamantane and its derivatives with tetrabromomethane catalyzed by iron compounds
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Catalytic bromination of adamantane and its derivatives with tetrabromomethane catalyzed by iron compounds has been performed. The favorable ratio of catalyst and reagents and the conditions of a selective synthesis of bromine-substituted adamantanes have been developed.
- Khusnutdinov,Shchadneva,Khisamova
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- Biocatalytic production of 5-hydroxy-2-adamantanone by P450cam coupled with NADH regeneration
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5-Hydroxy-2-adamantanone is a versatile starting material for the synthesis of various adamantane derivatives. In this study, we investigated the biocatalytic production of 5-hydroxy-2-adamantanone using P450cam monooxygenase coupled with NADH regeneration. We constructed Escherichia coli cells that expressed P450cam and its redox partners, putidaredoxin and putidaredoxin reductase, and cells that co-expressed this P450cam multicomponent system with a glucose dehydrogenase (Gdh) to regenerate NADH using glucose. Two types of cells - wet cells that did not receive any treatment after washing with glycerol-containing buffer, and freeze-dried cells that were lyophilized after the washing - were prepared as whole-cell catalysts. When wet cells were reacted with 2-adamantanone, E. coli cells expressing only the P450cam multicomponent system efficiently produced 5-hydroxy-2-adamantanone in the presence of glucose. However, the co-expression of this P450cam system with Gdh did not further enhance the amount of this product. These results indicate that enough amounts of NADH for P450cam catalysis would be supplied by endogenous glucose metabolism in the E. coli host. In contrast, when freeze-dried cells were used, only the cells co-expressing the P450cam multicomponent system with Gdh efficiently catalyzed the oxidation in the presence of glucose. These results suggest that the exogenous Gdh compensated loss of NADH regeneration by the endogenous glucose metabolism that would be damaged by the lyophilization process. Furthermore, we attempted to produce 5-hydroxy-2-adamantanone with repeated additions of the substrate using wet cells expressing only the P450cam multicomponent system and freeze-dried cells co-expressing this P450cam system with Gdh. These whole-cell catalysts attained high-yield production; the wet cells and the freeze-dried cells produced 36 mM (5.9 g/l) and 21 mM (3.5 g/l) of 5-hydroxy-2-adamantanone, respectively.
- Furuya, Toshiki,Kanno, Takaaki,Yamamoto, Hiroaki,Kimoto, Norihiro,Matsuyama, Akinobu,Kino, Kuniki
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- Reversal of diastereoselectivities in intra- and intermolecular reactions of 2-adamantanylidenes primarily caused by electron-donating and electron-withdrawing substituents on C5
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(Matrix presented) A reversal of diastereoselectivity was observed for novel 5-(trimethylsilyl)adamantan-2-ylidene (1c) with regard to 5-hydroxyadamantan-2-ylidene (1a). Ostensibly in intermolecular reactions, 5-substituted 2-adamantanylidenes (1) are ste
- Knoll, Wolfgang,Bobek, Michael M.,Kalchhauser, Hermann,Rosenberg, Murray G.,Brinker, Udo H.
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- Chemo- and regioselective oxidation of adamantyl derivatives by dioxiranes
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Methyl(trifluoromethyl) dioxirane (1) gives direct chemo- and regioselective oxidation of methyleneadamantane oxide (2) and isopropylideneadamantane oxide (3) in high yield under mild conditions. Secondary C-H are not appreciably oxidized and high regiose
- D'Accolti, Lucia,Kang, Ping,Khan, Saeed,Curci, Ruggero,Foote, Christopher S.
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- Chemoselectivity of Nitroxylation of Cage Hydrocarbons
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Abstract: The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic anhydride, and methylene chloride has been studied. More reactive substrates react with lowest
- Ivleva, E. A.,Klimochkin, Yu. N.,Leonova, M. V.
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p. 1702 - 1710
(2020/12/01)
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- 2, 4 -DIAMINOPYRIMIDINE DERIVATIVES AS PROTEIN KINASE INHIBITORS
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The present invention relates to novel pyrimide derivatives of formula (I): that are useful as kinase inhibitors. More particularly, the present invention relates to novel pyrimidine compounds, methods for their preparation, pharmaceutical compositions containing these compounds and uses of these compounds in the treatment of proliferative disorders.
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Page/Page column 68
(2012/05/20)
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- Intra- and intermolecular reaction selectivities of γ-substituted adamantanylidenes
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A study of adamantanylidenes having a γ-substituent (R) was undertaken to gauge how inductive and steric effects of remotely positioned functional groups influence intra- and intermolecular product selectivity. 3H-Diazirines were thermolyzed or photolyzed to generate the corresponding carbenes. On rapid heating, the resulting carbenes isomerized to 2,4-didehydroadamantanes by intramolecular 1,3-CH insertions. When R was an electron donor (RD) mostly asymmetric 1-substituted derivatives were produced but when it was an electron acceptor (RA) the symmetric 7-substituted ones were formed. When solutions were exposed to UV-A light, intermolecular adducts from the carbenes and solvent predominated with lesser amounts of intramolecular product being formed. Valence isomerization of 3H-diazirines also afforded diazo compounds. In methanol, protonation of diazo compounds to give the corresponding 2-adamantyl cations exceeds their coupling. This diversion was controlled with fumaronitrile by trapping the diazo compounds. The adducts possessed mostly anti configurations with R = R D and syn arrangements with R = RA. The connection between as- and anti-product formation and that of s- and syn-products was deemed to be the consequence of a rapid equilibrium between two distinct carbene conformations. This was qualified and quantified using ab initio calculations and NBO analyses.
- Knoll, Wolfgang,Kaneno, Daisuke,Bobek, Michael M.,Brecker, Lothar,Rosenberg, Murray G.,Tomoda, Shuji,Brinker, Udo H.
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experimental part
p. 1340 - 1360
(2012/03/27)
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- L -DIHYDRO-2-OXOQUINOLINE COMPOUNDS A 5-HT4 RECEPTOR LIGANDS
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The present invention relates to novel l,2-dihydro-2-oxoquinoline compounds of the formula (I), and their derivatives, prodrugs, tautomers, stereoisomers, polymorphs, solvates, hydrates, metabolites, N-oxides, pharmaceutically acceptable salts and compositions containing them. Formula (I) The present invention also relates to a process for the preparation of above said novel compounds, and their derivatives, prodrugs, tautomers, stereoisomers, polymorphs, solvates, hydrates, metabolites, N-oxides, pharmaceutically acceptable salts and compositions containing them. The compounds of the present invention are useful in the treatment/prevention of various disorders that are mediated by 5-HT4 receptor activity.
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Page/Page column 23-24
(2011/04/18)
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- 2 H-azirines from a concerted addition of alkylcarbenes to nitrile groups
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Photolysis of aziadamantanes in the presence of fumaronitrile (FN) unexpectedly afforded conjugated 2H-azirines resulting from addition of the carbene to the CN triple bond. This represents the first example of a direct azirine formation starting from an alkylcarbene for which a concerted pathway is postulated. The novel outcome of the reaction is favored by the prior formation of a carbene-alkene complex, a type of adduct that only recently has been described.
- Knoll, Wolfgang,Mieusset, Jean-Luc,Arion, Vladimir B.,Brecker, Lothar,Brinker, Udo H.
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supporting information; experimental part
p. 2366 - 2369
(2010/07/13)
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- Selective hydroxylation of adamantane and its derivatives
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A general method was developed for hydroxylation into the nodal position of adamantane and its 1- and 2-substituted derivatives employing systems H 2O-CBr4 (BrCCl3, CCl4) in the presence of complexes of Pd, Ni, Ru, Co, Mo, W, and Fe. The oxidants in the systems are hypochlorous (HOCl) or hypobromous (HOBr) acids generated from water and halomethanes under the reaction conditions.
- Khusnutdinov,Shchadneva,Mukhametshina,Dzhemilev
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scheme or table
p. 1137 - 1142
(2009/12/03)
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- Deuterated chemiluminescent 1,2-dioxetanes
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Deuterium-based i.e. isotopic hydrogen chemiluminescent 1,2-dioxetanes derived from the photo-oxidation of new novel alkenes which are synthesized by the coupling reaction of (a) a saturated or unsaturated cyclic, polycylic, normal or branched chain alkyl, cycloalkyl and spiro-fused and (b) substituted aromatic esters or ketones wherein (a) or (b) or both at least have a deuterium atom or a deuterium atom-containing group. These deuterium-based 1,2-dioxetanes may also have electron donating or withdrawing groups at the four-membered peroxide ring. Thus, the added electronic charge and the isotopic hydrogen or isotopic hydrogen-containing group hereof affects the light producing efficiency of 1,2-dioxetanes.
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Page/Page column 13
(2009/05/29)
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- Chemiluminescent 1,2-dioxetanes
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A method of generating light through chemiluminescence involves providing a stable 1,2-dioxetane of the formula: Wherein (a) R1 and R2 are each, individually, a chemical reactive site or when fused together form a chemical reactive site, and R3 and R4 are each, individually, a chemical reactive site or when fused together form a chemical reactive or (b) R1 has at least two hetero atoms with chemical reactive site and R3 and R4 are inactive site and R2 is a chemical reactive site.
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- NOVEL DIPEPTIDYL PEPTIDASE INHIBITORS AND PROCESSES FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
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The present invention relates to novel compounds representated by formula (I), where R, R1, R2, R3, X, Y, m, n are as defined.The present invention relates to compounds of the general formula I their derivatives, their analogs, their tautomeric forms, their stereoisomers, their diastereomers, their bioisosteres, their polymorphs, their pharmaceutically acceptable salts and pharmaceutically acceptable compositions containing them which are predominantly dipeptidyl peptidase IV inhibitors. The present invention also relates to the processes for the preparation of novel compounds of formula (I) and their use in treating type II diabetes and diabetic complications thereof and also for treating dislipidemia, hypercholesterolemia, obesity and hyperglycemia.
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Page/Page column 49
(2008/06/13)
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- Simple and efficient deprotection of 1,3-dithianes and 1,3-dithiolanes by copper(II) salts under solvent-free conditions
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Aerobic solid state deprotection of 1,3-dithianes and 1,3-dithiolanes of aromatic and aliphatic aldehydes and ketones has been performed in excellent yields by Cu(NO3)2·2.5H2O in the presence of montmorillonite K10 clay and sonic waves at room temperature. These dethioacetalizations proceed more slowly but efficiently under catalytic conditions by using 20% of the copper(II) salt with K10 clay and sonication.
- Oksdath-Mansilla, Gabriela,Pe?é?ory, Alicia B.
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p. 6150 - 6154
(2008/03/12)
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- Chemiluminescent 1,2-dioxetanes
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A method of generating light through chemiluminescence involves providing a stable 1,2-dioxetane of the formula: Wherein (a) R1 and R2 are each, individually, a chemical reactive site or when fused together form a chemical reactive site, and R3 and R4 are each, individually, a chemical reactive site or when fused together form a chemical reactive or (b) R1 has at least two hetero atoms with chemical reactive site and R3 and R4 are inactive site and R2 is a chemical reactive site.
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- Synthetic approach to preparation of polycyclic compounds possessing physiological activity: I. Synthesis of 1,4-disubstituted adamantanes with amino acid fragment
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In the present publication various synthetic procedures are reported for previously unknown 1,4-disubstituted adamantanes, containing in particular in position 1 an amino acid fragment (N-benzoyl-β-alanyloxy group). The procedures developed for modification of functional groups in the adamantane skeleton provide a possibility of synthesis of compounds with potential anticancer activity.
- Zefirova,Selyunina,Averina,Zyk,Zefirov
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p. 1125 - 1129
(2007/10/03)
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- Chemiluminescent 1,2-dioxetanes
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The present invention provides novel 1,2-dioxetanes derived from spiro-fused ketones with or without π-electrons in the ring or with carbon-carbon double bond(s) in the spiro-fused ring. Additionally, these new dioxetanes have electron donating or withdrawing groups at the four-membered peroxide ring to render these dioxetanes active at all sites.
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- 4-oxatricyclo[4.3.1.1 3,8]undecan-5-one derivative and process for producing the same
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A 4-oxatricyclo[4.3.1.13,8]undecan-5-one derivative is shown by the following formula (1): wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. This compound is a novel 4-oxatricyclo[4.3.1.13,8]undecan-5-one derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position.
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- Methods of acylating adamantane, tricyclo[5.2.1.02,6], and decalin compounds
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An acylating agent of the invention includes (A) a 1,2-dicarbonyl compound or its hydroxy reductant, (B) oxygen, and (C) at least one compound selected from (c1) a metallic compound and (C2) N-hydroxyphthalimide or another imide compound. As the 1,2-dicarbonyl compound or its hydroxy reductant (A), biacetyl, 2,3-butanediolor the like canbeused. As the metallic compound (c1), cobalt acetate, or another cobalt compound, for example, can be employed. By reacting an adamantane derivative or another compound having a methine carbon atom with the acylating agent, an acyl group can be introduced to the methine carbon atom with efficiency.
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- Process for the preparation of hydroxyadamantanone derivatives
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The invented process produces a corresponding 5-hydroxy-2-adamantanone derivative by allowing a 2-adamantanone derivative of the following formula (1): wherein each of Ra, Rb, and Rcis, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, or a nitro group, and of carbon atoms constituting an adamantane skeleton, the other carbon atoms than carbon atoms at bridgehead positions and at a bonding position of an oxo group may have a substituent, to react with oxygen in the presence of N-hydroxyphthalimide or another imide compound, a vanadium compound, and a manganese compound.
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- A facile one-step synthesis of 2,4-adamantanedione
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2,4-Adamantanedione (2) can be synthesized in one step by direct oxidation of adamantanone with a pyridine-chromium trioxide complex in acetic anhydride in 54% isolated yield.
- Bobek, Michael M.,Brinker, Udo H.
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p. 3221 - 3225
(2007/10/03)
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- AMINO BI- AND TRI-CARBOCYCLIC AKLANE BIS-ARYL SQUALENE SYNTHASE INHIBITORS
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This invention relates to a class of novel amino bi- and tri-carbocyclic alkane compounds having bis-aryl substitution which exhibit squalene synthase inhibition properties. The bi- and tri-carbocyclic alkane ring contains an amino group and the ring is further linked or bridged to two mono- and/or bicyclic rings. Compounds of this invention reduce levels of serum cholesterol in the body without significantly reducing mevalonic metabolite synthesis. This invention relates also to pharmacological compositions and method of treatment for lowering serum cholesterol levels using the compounds of this invention.
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- Spiro[isoxazalidine-3,2'-tricyclo[3.3.1.13,7 ] decanes]
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The compounds are of the class of adamantanyl isoxazolidine derivatives useful as anti-inflammatory, antihypoxia, antimicrobial and anticonvulsant agents. Exempliary of a species of the compounds is 2 methyl-5-n-hexyl-spiro[isoxazolidin-3,2'-tricyclo[3.3.1.13,7 ] decane].
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- 5-HYDROXYADAMANTAN-2-ONE
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An improved, convenient and rapid procedure is described for the conversion of adamantanone into the title compound on a multigram scale in 60percent yield.
- Srivastava, S.,Noble, W. le
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- Fluorination of Adamantane Derivatives with Oxygen Difluoride
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Fluorination of adamantane and adamantane derivatives 1 with OF2 in the absence of an HF-trap gives fluoroadamantanes 2 and adamantanols 3 in varying amounts.Increasing yields of 2 are obtained in the presence of Na2CO3 as an HF-trap.In addition, the fluorooxahomoadamantanes 4b and e are formed in this reaction.The fluorination of adamantanone (5) with OF2 leads to analogous products.
- Bolte, Gerd,Haas, Alois
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p. 1982 - 1986
(2007/10/02)
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