- Electrophotochemical Ring-Opening Bromination oftert-Cycloalkanols
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An electrophotochemical ring-opening bromination of unstrainedtert-cycloalkanols has been developed. This electrophotochemical method enables the oxidative transformation of cycloalkanols with 5- to 7-membered rings into synthetically useful ω-bromoketones without the use of chemical oxidants or transition-metal catalysts. Alkoxy radical species would be key intermediates in the present transformation, which generate through homolysis of the O-Br bond in hypobromite intermediates under visible light irradiation.
- Yamamoto, Kosuke,Toguchi, Hiroyuki,Kuriyama, Masami,Watanabe, Shin,Iwasaki, Fumiaki,Onomura, Osamu
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p. 16177 - 16186
(2021/09/13)
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- Iodobenzene-catalyzed oxidative cleavage of olefins to carbonyl compounds
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A metal-free approach for the oxidative cleavage of carbon–carbon double bonds of olefins to carbonyl compounds was established by using oxidant m-CPBA and non-metallic organocatalyst PhI in toluene/H2O. A broad scope of aromatic olefins was used. All the reactions proceeded smoothly at 35 °C in short reaction time to furnish the respective mono- and double carbonyl compounds selectively in moderate to good yields.
- Du, Lele,Wang, Zechao,Wu, Junliang
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supporting information
(2020/07/20)
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- Triphosgene and DMAP as Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols
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The utility of triphosgene and DMAP as mild reagents for chemoselective dehydration of tertiary alcohols is reported. Performed in dichloromethane at room temperature, this reaction is readily tolerated by a broad scope of substrates, yielding alkenes preferentially with the (E)-geometry. While formation of the Hofmann products is generally favored, a dramatic change in alkene selectivity toward the Zaitzev products is observed when the reaction is carried out in dichloroethane at reflux.
- Ganiu, Moshood O.,Cleveland, Alexander H.,Paul, Jarrod L.,Kartika, Rendy
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supporting information
p. 5611 - 5615
(2019/08/01)
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- Azetidine derivatives and synthesis method thereof
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The invention belongs to the field of chemical synthesis, and discloses an azetidine derivative and a synthesis method thereof. The structural formula of the target product azetidine derivatives is asshown in formulae (I), (II), (III), (IV) and (V). The compounds of the formulae are compounds containing an azetidine skeleton, and a nitrogen atom in the skeleton is protected by 2-picolinic acid. The target product azetidine derivatives can be: azetidinyl amide derivatives, azabicyclo[x.1.1] amide derivatives (x=3, 4, 5, 6, 7, 8, 9), azabicyclo[4.1.1] amide derivatives having a substituent at the ring, azabicyclo[4.2.0] amide derivatives and azetidine derivatives containing spirocyclic quaternary carbon. The azetidine derivatives of the present invention have certain protective effect on hydrogen peroxide-induced oxidative stress damage of HC cells.
- -
-
Paragraph 0072-0074; 0075-0077
(2019/03/26)
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- Polycyclic Azetidines and Pyrrolidines via Palladium-Catalyzed Intramolecular Amination of Unactivated C(sp3)-H Bonds
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A novel strategy to construct complex polycyclic nitrogen-containing heterocycles from aliphatic amines via picolinamide-assisted palladium-catalyzed C-H bond activation reaction was reported. The reaction exhibits broad substrate scope for the synthesis of various azabicyclic scaffolds, including azetidines and tropane-class alkaloids. Application of this method to naturally occurring (-)-cis-myrtanylamine, an unprecedented type of carbon-carbon bond activation, in which the electron-pair involved initiates an intramolecular "SN2-like" displacement of a cyclopalladium-fragment from a tertiary center, is described.
- Zhao, Jie,Zhao, Xiao-Jing,Cao, Pei,Liu, Ji-Kai,Wu, Bin
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supporting information
p. 4880 - 4883
(2017/09/23)
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- Auto de-bromine-coupling reactions of 1-aryl-7-bromocycloheptenes
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Auto de-bromine-coupling reactions of 1-aryl-7-bromocycloheptenes to a new series of [7-6-6] tricyclic system were described. A variety of substituents at the para-position of the phenyl were amenable to this transformation, including electron-donating groups and halides. The presence of electron-donating groups resulted in a more efficient reaction, with higher yields than the case of halides.
- Lee, Gon-Ann,Lee, Hsin-Yi,Wang, Wen-Chieh,Cherng, Chih-Hwa
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p. 2956 - 2961
(2014/04/17)
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- Syntheses and N-methyl-D-aspartate receptor antagonist pharmacology of fluorinated arylcycloheptylamines
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Selective uncompetitive antagonists of the phencyclidine (PCP) binding site of the N-methyl-D-aspartate receptor (NMDAR) are known to have therapeutic potential as anticonvulsants and neuroprotective agents. Several fluorinated molecules with each containing a cycloheptane ring were designed to probe the PCP pharmacophore and test the influence of fluorine substitution on NMDAR binding and in vivo efficacy. Syntheses and analyses of six novel compounds, 1-(4-fluorophenyl)cycloheptanamine (3), 1-(1-(4-fluorophenyl)cycloheptyl)piperidine (4), 1-(1-(4-fluorophenyl)cycloheptyl) pyrrolidine (5), 1-(3-fluorophenyl)cycloheptanamine (6), 1-(1-(3-fluorophenyl)cycloheptyl)piperidine (7), 1-(1-(3-fluorophenyl)cycloheptyl)pyrrolidine (8) and several related reference arylcyloalkylamines are described. Receptor binding was performed at the PCP site of NMDAR for each compound using [3H]-(+)-MK-801 displacement. Unexpectedly, the 3-fluoro-primary amine 6 had the greatest affinity of the series and these binding results support a different structure activity relationship (SAR) profile for arylcycloheptylamines when compared to arylcyclohexylamines like PCP. Five of the novel compounds have affinity (Ki) in the hundred nM (10-7) range. In addition, compounds 3, 5, 6, 7 and 8 were evaluated and found to exhibit neuroprotective effects from NMDA induced toxicity in vitro and compounds 6, 7 and 8 exhibited anticonvulsant activities in rats. An ED50 of 13.84 mg/kg was found for compound 6 in rat maximal electroshock (MES) test with a protective index (PI) of 3.66 against ataxia. These results support further investigation of the arylcycloheptylamine class.
- Sun, Shengguo,Wallach, Jason,Adejare, Adeboye
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p. 843 - 852
(2015/04/14)
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- The design of a novel series of muscarinic receptor antagonists leading to AZD8683, a potential inhaled treatment for COPD
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A novel series of muscarinic receptor antagonists was developed, with the aim of identifying a compound with high M3 receptor potency and a reduced risk of dose-limiting side effects with potential for the treatment of COPD. Initial compound mo
- Mete, Antonio,Bowers, Keith,Bull, Richard J.,Coope, Helen,Donald, David K.,Escott, Katherine J.,Ford, Rhonan,Grime, Ken,Mather, Andrew,Ray, Nicholas C.,Russell, Vince
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p. 6248 - 6253
(2013/11/19)
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- Rhodium(I)/diene-catalyzed addition reactions of arylborons with ketones
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Rh(I)/diene-catalyzed addition reactions of arylboroxines/arylboronic acids with unactivated ketones to form tertiary alcohols in good to excellent yields are described. By using C2-symmetric (3aR,6aR)-3,6-diaryl-1,3a,4,6a- tetrahydropentalenes as ligands, the asymmetric version of such an addition reaction, with up to 68% ee, was also realized.
- Liao, Yuan-Xi,Xing, Chun-Hui,Hu, Qiao-Sheng
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supporting information; experimental part
p. 1544 - 1547
(2012/06/05)
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- Controlled alcohol-carbonyl interconversion by nickel catalysis
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All in one pot: A general synthetic platform allows the interconversion of alcohols and carbonyl compounds in a predictable and controlled fashion in one pot. Under the action of a Ni catalyst, PhCl, CsF, and arylboronates, several multistep alcohol-carbonyl interconversions have been achieved with good overall efficiency (see scheme). A one-pot nickel-catalyzed synthesis of flumecinol (a hepatic microsomal enzyme inducer) has also been demonstrated. Copyright
- Maekawa, Takehisa,Sekizawa, Hiromi,Itami, Kenichiro
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p. 7022 - 7026
(2011/09/30)
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- QUINUCLIDINE DERIVATIVES AS MUSCARINIC M3 RECEPTOR ANTAGONISTS
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The invention provides named compounds of formula (I), wherein R4 is a N-substituted quinuclidine (I) pharmaceutical compositions containing them and a process for preparing the pharmaceutical compositions. Their use in therapy for’ the treatment of conditions mediated by M3 muscarinic receptors, such as chronic obstructive pulmonary disease is also disclosed.
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Page/Page column 11
(2011/08/02)
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- QUINUCLIDINE DERIVATIVES AS MUSCARINIC M3 RECEPTOR ANTAGONISTS
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The invention provides named compounds of formula (I ), wherein R4 is a N- sustituted quinuclidine ( I ) pharmaceutical compositions containing them and a process for preparing the pharmaceutical compositions. Their use in therapy for' the treatment of conditions mediated by M3 muscarinic receptors, such as chronic obstructive pulmonary disease is also disclosed.
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Page/Page column 31
(2009/12/23)
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- QUINUCLIDINE DERIVATIVES AND THEIR USE AS MUSCARINIC RECEPTOR ANTAGONISTS FOR THE TREATMENT OF ASTHMA AND CHRONIC OBSTRUCTIVE PULMONARY DISEASE (COPD)
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The invention provides compounds of formula (I) wherein R1, R2, R3, R4, R5, Het1, n, Y and X are as defined in the specification, a process for their preparation, pharmaceutical compositions containing them, a process for preparing pharmaceutical compositions, their use in therapy and intermediates of use in their preparation.
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Page/Page column 38
(2009/12/23)
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- NOVEL COMPOUNDS 514
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The invention provides compounds of formula (I), wherein R1, R2, R3, R4, R5, g, h and X are as defined in the specification, a process for their preparation, pharmaceutical compositions containing the
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Page/Page column 41
(2008/12/05)
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- QUINICLIDINE DERIVATIVES OF (HETERO) ARYLCYCLOHEPTANECARBOXYLIC ACID AS MUSCARINIC RECEPTOR ANTAGONISTS
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The invention provides compounds of formula (I) wherein R4 is a group of formula (II) or (IIIa) or (IIIb) and R1, R2, R3, R5, a, b and X are as defined in the specification, a process for their preparation, pharmaceutical compositions containing them, a process for preparing pharmaceutical compositions, their use in therapy and intermediates of use in their preparation (I), (II), (IIIa), (IIIb).
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Page/Page column 43-44
(2008/12/05)
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- Photolysis of 1-alkylcycloalkanols in the presence of (diacetoxyiodo) benzene and I2. Intramolecular selectivity in the β-scission reactions of the intermediate 1-alkylcycloalkoxyl radicals
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The C-C β-scission reactions of 1-alkylcycloalkoxyl radicals, generated photochemically by visible light irradiation of CH2Cl 2 solutions containing the parent 1-alkylcycloalkanols, (diacetoxy)-iodobenzene (DIB), and I2, have been investigated through the analysis of the reaction products. The 1-alkylcycloalkoxyl radicals undergo competition between ring opening and C-alkyl bond cleavage as a function of ring size and of the nature of the alkyl substituent. With the 1-propylcycloheptoxyl, 1-propylcyclooctoxyl, and 1-phenylcyclooctoxyl radicals, formation of products deriving from an intramolecular 1,5-hydrogen atom abstraction reaction from the cycloalkane ring has also been observed. The results are discussed in terms of release of ring strain associated to ring opening, stability of the alkyl radical formed by C-alkyl cleavage, and with cycloheptoxyl and cyclooctoxyl radicals, also in terms of the possibility of achieving a favorable geometry for intramolecular hydrogen atom abstraction.
- Antunes, Carla S. Aureliano,Bietti, Massimo,Lanzalunga, Osvaldo,Salamone, Michela
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p. 5281 - 5289
(2007/10/03)
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- Oxidative fragmentation of 1-aryl-1-cycloalkenes using cerium(IV) ammonium nitrate (CAN): Some novel observations
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1-Phenyl-1-cycloalkenes undergo oxidative fragmentation in presence of CAN in methanol, affording 1,n-dicarbonyl compounds as the major products along with 1,2-dimethoxycycloalkanes. The reaction under deoxygenated conditions afforded the latter in good yields. In the presence of azide ion, fragmentation leading to the corresponding cyanoketones was observed whereas with sulfinate only the 1-methoxy-2-sulfonyl cycloalkanes were formed.
- Nair, Vijay,Panicker, Sreeletha B,Thomas, Siji,Santhi,Mathai, Sindhu
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p. 3229 - 3234
(2007/10/03)
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- 13C NMR spectroscopic comparison of sterically stabilized meta and para-substituted o-tolyldi(adamant-l-yl)methyl cations with conjugatively stabilized benzyl cations
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A series of meta- and para-substituted anti-o-tolyldi(adamant-1-yl)methyl cations has been generated by reaction of anti-o-tolyldi(adamant-1-yl)methanols with trifluoroacetic acid in chloroform. 13C NMR spectroscopy indicates small but significant variations in the chemical shifts of the charged carbon and its nearest neighbours on the adamantyl groups, and departures from additivity of substituent effects on the shifts of the aromatic carbons. Previous work on the closely related di(adamant-1-yl)benzyl cations is discussed. Comparison with data on aryl-substituted carbocations in superacid media reveals marked differences in the aromatic carbon shifts in the two types of carbocation. The dihedral angle between aryl and carbocation planes in aryldi(adamant-1-yl)methyl cations is estimated to be about 60°.
- Lomas, John S.
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p. 2601 - 2609
(2007/10/03)
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- Synthesis of Certain Mesogenic Azomethines Derived from 4-Cycloalkylanilines and from 4-Cycloalkylbenzaldehydes
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General procedures are described for the synthesis of members of five pairs of related homologous series of mesogenic azomethines differing in the mode of linkage of the CH=N group and containing a cycloalkyl group in a terminal position.
- Byron, D. J.,Matharu, A. S.,Rees, M.,Wilson, R. C.
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p. 229 - 238
(2007/10/02)
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- Side Chain Hydroxylation of Aromatic Compounds by Fungi. Part 5. Exploring the Benzylic Hydroxylase of Mortierella isabellina
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The active site topography of the hydroxylase enzyme of Mortierella isabellina ATCC 42613, which carries out the benzylic hydroxylation of toluene, ethylbenzene, and related compounds, has been explored.Operating in a whole cell biotransformation mode, this enzyme shows selectivity in substrate processing based on the nature, position and size of substituent side chains close to the site of hydroxylation.The results of determination of the yield and stereochemistry of hydroxylation of over twenty substrates and potential substrates, together with previously reported data, have been used to propose an active site model for the benzylic hydroxylase enzyme.
- Holland, Herbert L.,Kindermann, Maik,Kumaresan, Sudalaiyandi,Stefanac, Tomislav
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p. 1353 - 1364
(2007/10/02)
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- Synthesis and Anticonvulsant Activity of 1-Phenylcyclohexylamine Analogues
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Thirty-eight analogues of 1-phenylcyclohexylamine (PCA), a phencyclidine (PCP) derivative, were examined for their activities in the mouse maximal electroshock (MES) seizure test and in a motor-toxicity assay.In addition, we determined the binding affinities of the compounds for PCP acceptor sites in rat brain membranes labeled with -1-piperidine.Many of the analogues were protective against MES seizures (ED50s of 4-41 mg/kg, ip) and all of these compounds caused motor toxicity.The potencies in the motor toxicity and MES seizure tests showed a moderate correlation with the affinities for PCP sites.Several analogues exhibited a greater separation of potencies in the motor toxicity and MES seizure tests than did the parent compound PCA.These were obtained by (i) 3-methylation of the cyclohexyl ring trans to the phenyl ring, (ii) methoxylation at the ortho position on the phenyl ring, and (iii) contraction of the cyclohexane ring to form the corresponding cyclopentane.
- Thurkauf, Andrew,Costa, Brian de,Yamaguchi, Shun-ichi,Mattson, Mariena V.,Jacobson, Arthur E.,et al.
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p. 1452 - 1458
(2007/10/02)
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- Studies on the Oxidation of Phenyl Cycloalkanes by Tertiary Hydroperoxides
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During the thermal decomposition of cumene hydroperoxide at about 125 deg C in phenyl cycloalkanes as solvents, the solvents are attacked, preferably at the tertiary C-H bonds.Up to 70percent (with regard to the decomposed hydroperoxide) of oxidation products of the phenyl cycloalkanes are obtained.The main oxidation products are the corresponding 1-phenyl cycloalkanols, but relatively large amounts of phenyl alkyl ketones with the same number of carbon atoms are also formed, probably via a further oxidation of the 1-phenyl cycloalkanols.
- Pritzkow, Wilhelm,Suprun, Vladimir Ya.,Voerckel, Volkmar
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p. 381 - 386
(2007/10/02)
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- Studies on the Autoxidation of Phenyl Cycloalkanes
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The products of the autoxidation of phenyl cyclopropane (I), phenyl cyclobutane (II), phenyl cyclopentane (III), phenyl cyclohexane (IV), phenyl cycloheptane (V) and phenyl cyclooctane (VI) were analyzed after reduction of the reaction mixtures with LiAlH4.As products of the attack on the α-C-H bonds the corresponding 1-phenyl cycloalkanols and 1-phenyl alkan-1-ols were found.In the case of phenyl cyclopropane some SR2 ring opening probably takes place.The oxidabilities , the chain termination constants kt, the absolute chain propagation constants kp and the relative chain propagation constants (kp)rel were determined for the phenyl cycloalkanes I-VI.As it is to be expected on the basis of the I-strain concept the autoxidation rate of phenyl cyclopentane (III) is considerably higher than that of phenyl cyclobutane (II) and phenyl cyclohexane (IV).
- Batke, Birgit,Lauterbach, Gerlinde,Pritzkow, Wilhelm,Voerckel, Volkmar,Belyakov, Vladimir A.
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p. 424 - 430
(2007/10/02)
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- CH ACIDITY OF SUBSTITUTED CYCLOALKANES. I. KINETIC ACIDITY OF PHENYLCYCLOALKANES
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The kinetic acidities of phenylcycloalkanes were determined in a solution of lithium cyclohexylamide in cyclohexylamine.The obtained values are compared with the analogous values for cycloalkanes and with the heats of hydrogenation of methylenecycloalkanes.The introduction of the phenyl substituent increases the proton mobility of the hydrogen in the cycloalkanes.A relation was established between the kinetic acidity of the phenylcycloalkanes and the strain in the alkane rings of their carbanions.
- Zharova, N. G.,Shapiro, I. O.,Shatenshtein, A. I.
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p. 211 - 214
(2007/10/02)
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- Studies on Thermal Conversion of Phenylcyclopentane, -hexane, -heptane, and -octane in the Gas Phase
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The title compounds were pyrolyzed from 700 to 780 deg C in a metallic laboratory tubular reactor in the presence of steam.The reaction products were analyzed by gas chromatography and by a combination of gas chromatography and mass spectrometry.From the phenylcyclanes tested, more than 65 hydrocarbons could be detected in the liquids, besides gaseous reaction products.In most cases unambiguous structures could be derived by using different analytical methods.As typical initial-step products phenylcyclenes, ω-phenyl-1-alkenes and 1-phenyl-1-alkenes are formed by dehydrogenation and isomerization of the title compounds.The detection of phenylalkenes corresponds well with the isomerization of unsubstituted cyclanes to the corresponding α-olefines described in former papers.
- Lam, Ho Son,Zimmermann, G.,Anders, G.,Bach, G.,Rennecke, D.,Zychlinski, W.
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p. 759 - 766
(2007/10/02)
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