- A Mild Heteroatom (O -, N -, and S -) Methylation Protocol Using Trimethyl Phosphate (TMP)-Ca(OH) 2Combination
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A mild heteroatom methylation protocol using trimethyl phosphate (TMP)-Ca(OH)2combination has been developed, which proceeds in DMF, or water, or under neat conditions, at 80 °C or at room temperature. A series of O-, N-, and S-nucleophiles, including phenols, sulfonamides, N-heterocycles, such as 9H-carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl thiols, are suitable substrates for this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmentally friendly nature of this protocol make it an attractive alternative to the conventional base-promoted heteroatom methylation procedures.
- Tang, Yu,Yu, Biao
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- Conversion of Cyclohexanones to Alkyl Aryl Ethers by Using a Pd/C–Ethylene System
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The conversion of cyclohexanone and substituted cyclohexanones into alkyl aryl ethers by using a Pd/C–ethylene system is discussed, with ethylene functioning as a hydrogen acceptor. The ether products are easily transformed into the corresponding phenols by treatment with BBr3. The direct conversion of cyclohexenone into phenol in the presence of a catalytic amount of Pd/C under an ethylene atmosphere is also described.
- El-Deeb, Ibrahim Yussif,Tian, Miaomiao,Funakoshi, Tatsuya,Matsubara, Ryosuke,Hayashi, Masahiko
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supporting information
p. 409 - 413
(2017/01/24)
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- A Divergent Approach to the Diastereoselective Synthesis of 3,3-Disubstituted Oxindoles from Atropisomeric N-Aryl Oxindole Derivatives
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3,3-Disubstituted oxindoles were divergently synthesized by diastereoselective transformations including nucleophilic addition, alkylation, and cycloaddition using common, axially chiral N-aryl oxindoles. Notably, high diastereoselectivities (up to >95:5) were observed with ortho-monosubstituted N-aryl oxindoles to give various oxindole scaffolds, and facile removal of the p-(benzyloxy)aryl moiety in axially twisted amides was achieved by a mild, two-step sequence.
- Nakazaki, Atsuo,Mori, Ayako,Kobayashi, Susumu,Nishikawa, Toshio
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supporting information
p. 3267 - 3274
(2016/11/29)
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- Methylation of phenol and its derivatives with dimethyl carbonate in the presence of Mn2(CO)10, W(CO)6, and Co2(CO)8
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Aryl methyl ethers were synthesized by reactions of phenol, substituted phenols, and α- and β-naphthols with dimethyl carbonate in the presence of manganese, tungsten, and cobalt carbonyls. Optimal reactant and catalyst ratios and reaction conditions were found to ensure selective formation of aryl methyl ethers.
- Khusnutdinov,Shchadneva,Mayakova, Yu. Yu.
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p. 330 - 334
(2015/05/04)
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- DEUTERATED BENZOPYRAN COMPOUND AND APPLICATION THEREOF
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features as shown in Formula (I), or pharmaceutically acceptable salts or stereoisomers thereof, or prodrug molecules thereof. With excellent anti-inflammatory and analgesic effects and the capability to inhibit growth of tumor cells, such compounds are novel COX-2 selective inhibitors. The compounds and pharmaceutically acceptable salts thereof disclosed by the present application can be applied in preparing anti-inflammatory and analgesic drugs and drugs for treating or preventing tumors.
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Paragraph 0101-0102
(2015/03/18)
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- Deuterated Benzopyran Compounds and Application Thereof
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The present invention discloses deuterated benzopyran compounds having structure features as shown in Formula (I), or pharmaceutically acceptable salts or stereoisomers thereof, or prodrug molecules thereof. With excellent anti-inflammatory and analgesic effects and the capability to inhibit growth of tumor cells, such compounds are novel COX-2 selective inhibitors. The compounds and pharmaceutically acceptable salts thereof disclosed by the present application can be applied in preparing anti-inflammatory and analgesic drugs and drugs for treating or preventing tumors.
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Paragraph 0208-0211; 0232-0235; 0337-0340
(2015/05/26)
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- A highly active and selective palladium pincer catalyst for the formation of α-aryl ketones via cross-coupling
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Several air and moisture stable Pd(ii) pincer complexes were synthesized via oxidative addition of Pd(0) to novel PheBox pincer ligand precursors. Low loadings (1 mol%) of the Pd complex [t-BuPhebox-Me2]PdBr are capable of efficiently promoting the selective α-monoarylation of a variety of ketones with numerous aryl bromides in only 1 h at 70°C with 82-99% yields.
- Bugarin, Alejandro,Connell, Brian T.
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supporting information; experimental part
p. 7218 - 7220
(2011/08/09)
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- Structure-activity relationship analysis of Pd-PEPPSI complexes in cross-couplings: A close inspection of the catalytic cycle and the precatalyst activation model
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A series of Pd-N-heterocyclic carbene (Pd-NHC) complexes with various NHC, halide and pyridine ligands (PEPPSI (pyridine, enhanced, precatalyst, preparation, stabilisation and initiation) precatalysts) were prepared, and the effects of these ligands on catalyst activation and performance were studied in the Kumada-TamaoCorriu (KTC), Negishi, and Suzuki-Miyaura cross-coupling reactions. The lowered reactivity of more hindered 2,6-dimethylpyridyl complex 4 in the Negishi and KTC reactions is consistent with slow reductive dimerisation of the organometallic reaction partner during precatalyst activation. Comparative rate studies of complexes 1, 4 and 5 in the KTC and Suzuki-Miyaura reactions verify that 4 activated more slowly than the others. A potential on/ off mechanism of pyridine coordination to NHC-Pd0 is also plausible, in which the more basic pyridine stays bound for longer.
- Nasielski, Joanna,Hadei, Nilofaur,Achonduh, George,Kantchev, Eric Assen B.,O'Brien, Christopher J.,Lough, Alan,Organ, Michael G.
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supporting information; scheme or table
p. 10844 - 10853
(2010/12/19)
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- Synthesis of novel structurally simplified estrogen analogues with electron-donating groups in ring A
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A library of 25 novel estrogen analogues were prepared in five to eight steps from mostly commercially available substituted anisoles via bromination, formylation, Corey-Fuchs reaction, elimination, and Sonogashira reaction. Georg Thieme Verlag Stuttgart.
- Tietze, Lutz F.,Vock, Carsten A.,Krimmelbein, Ilga K.,Nacke, Linda
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experimental part
p. 2040 - 2060
(2009/12/27)
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- Eco-friendly hydrodehalogenation of electron-rich aryl chlorides and fluorides by photochemical reaction
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Aryl chlorides and fluorides are smoothly hydrodehalogenated by irradiation either in neat i-PrOH or in a polar solution in the presence of hypophosphorous acid or triethylsilane. The procedure gives the halogen-free products in good to excellent yields under mild eco-friendly conditions and avoids the recourse to toxic metal catalysts.
- Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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experimental part
p. 942 - 945
(2010/04/23)
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- SUBSTITUTED OXAZOLIDINONES
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The present invention relates to new oxazolidinone modulators of skeletal muscle function and tone, pharmaceutical compositions thereof, and methods of use thereof.
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Page/Page column 28
(2009/10/31)
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- An efficient intermolecular BINAM-copper(I) catalyzed Ullmann-type coupling of aryl iodides/bromides with aliphatic alcohols
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A wide range of alkyl aryl ethers are synthesized from the corresponding aryl iodides and aliphatic alcohols through Ullmann-type intermolecular coupling reactions in the presence of a catalytic amount of easily available BINAM-CuI complex. Less reactive aryl bromides have also been shown to react with aliphatic alcohols under identical reaction conditions to give good yields of the alkyl aryl ethers without increasing the reaction temperature and time.
- Naidu, Ajay B.,Sekar
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p. 3147 - 3151
(2008/09/20)
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- Metal-free synthesis of sterically crowded biphenyls by direct Ar-H substitution in alkyl benzenes
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(Chemical Equation Presented) Four's definitely a crowd: The chemoselective activation of Ar-H bonds in methylbenzenes by treatment with photogenerated phenyl cations allowed the synthesis of sterically crowded biphenyl compounds, including tetra-ortho-substituted biphenyls, by intermolecular cross-coupling (see scheme). This method is an appealing metal-free alternative to widely used transition-metal catalysis. TFE = 2,2,2-trifluoroethanol.
- Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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p. 6495 - 6498
(2008/09/16)
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- Solid state S-methylation of thiols and O-methylation of phenols and naphthols with dimethyl sulfate under microwave irradiation
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Mild and efficient S-methylation of thiols and o-methylation of phenols and naphthals occurs with dimethyl sulfate (DMS) supported on basic alumina under microwave irradiation in solventless system. Copyright Taylor & Francis Inc.
- Heravi, Majid M.,Ahari, Neda Zamani,Oskooie, Hossein A.,Ghassemzadeh, Mitra
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p. 1701 - 1712
(2007/10/03)
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- New 2,2′-substituted 4,4′-dimethoxy-6,6′-dimethyl[1, 1′-biphenyls], inducing a strong helical twisting power in liquid crystals
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Based on the stabilisation of the molecular motion by the chiral residue, novel optically active biphenylic chiral dopants for nematic liquid crystals were developed. This molecular congestion was obtained by introducing mesogenic residues on the 2,2′-positions of the chiral biphenyl; this led to a novel molecular architecture that was found to be efficient. The synthesised optically active biphenyls were characterised with very short cholesteric pitches when used as chiral dopants in nematic liquid crystals. The synthesis of the enatiomerically pure biphenyl dopants and their preliminary physicochemical characterisations are described.
- Holzwarth, Richard,Bartsch, Richard,Cherkaoui, Zoubair,Solladie, Guy
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p. 3931 - 3935
(2007/10/03)
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- Synthesis and cytotoxic activity of tetracenomycin d and of saintopin analogues
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Regiospecific synthesis of title compounds is based either on cycloaddition of ketene acetals derived from Hagemann's ester or of homophthalic anhydrides. Thus, tetracenomycin D and 3,8-di-O-methyl saintopin have been prepared in few steps. New derivatives of 10-deoxysaintorpin have been also obtained. Evaluation of their cytotoxicity against L1210 leukemia cells are reported. Copyright
- Martin, Philippe,Rodier, Stephane,Mondon, Martine,Renoux, Brigitte,Pfeiffer, Bruno,Renard, Pierre,Pierre, Alain,Gesson, Jean-Pierre
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p. 253 - 260
(2007/10/03)
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- A Pyrolytic Approach to 2-Hydroxy-7-methoxy-5-methyl-1-naphthoic Acid
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Condensation of 4-methoxy-2,6-dimethylbenzaldehyde with Meldrum's acid, and flash vacuum pyrolysis of the condensation product (12) gave in almost quantitative yield 7-methoxy-5-methyl-2-naphthol (9).This naphthol is a precursor of the title 1-carboxylic acid (6), an intercalating moiety of enediyne and other antibiotics.
- Brown, Roger F. C.,Eastwood, Frank W.,Horvath, Julianna
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p. 1055 - 1058
(2007/10/02)
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- Hindered organoboron groups in organic chemistry. 27. Preparations and some properties of alkylbis(2,6-dimethyl-4-methoxyphenyl)boranes ((DMP)2BR)
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Akylbis(2,6-dimethyl-4-methoxyphenyl)boranes ((DMP)2BR) have been synthesized in an attempt to overcome the limitations of the steric hindrance approach to the production of boron stabilised carbanions. Anion production from (DMP)2BR, followed by alkylations and condensations with aldehydes are reported. Reduction of (DMP)2F with potassium hydride yields the corresponding hydroborate. Attempts to isolate (DMP)2BH were unsuccessful but the borane was readily trapped with alkynes, yielding alkenylboranes. The allyl derivative, (DMP)2BAllyl, was made and some of its reactions were investigated.
- Pelter, Andrew,Drake, Robert
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p. 13775 - 13800
(2007/10/02)
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- Correlation of Reaction Rates with a Substituent Constant Scale Derived from Calculated Electron Densities for a Computer Control Algorithm
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A new ? substituent scale based on electron density calculations by the AM1 quantum mechanical model has been established and used to correlate rates of O-methylation of substituted phenols, as part of a chemical artificial intelligence to control a fully automated apparatus for methyl iodide labeling.
- Cork, David G.,Hayashi, Nobuyoshi
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p. 1583 - 1585
(2007/10/02)
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- New Oxidative Aromatization of α,β-Unsaturated Cyclohexenones with Iodine-Cerium(IV) Ammonium Nitrate in Alcohol
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The reaction of 2-cyclohexen-1-one derivatives with iodine-cerium(IV) ammonium nitrate in alcohols (methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol) under refluxing, gave the corresponding alkyl phenyl ethers in good yields.In the case of diol (ethylene glycol, 1,3-propanediol, and 1,4-butanediol), phenoxyalkanol derivatives were obtained.The present method was also applicable to oxidative rearrangement of isophorone.
- Horiuchi, C. Akira,Fukunishi, Hirotada,Kajita, Mika,Yamaguchi, Akihisa,Kiyomiya, Hiroshi,Kiji, Shinji
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p. 1921 - 1924
(2007/10/02)
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- AGGREGATION OF LITHIUM PHENOLATES IN WEAKLY POLAR APROTIC SOLVENTS.
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The aggregation of lithium phenolate, 3,5-dimethylphenolate, 2,6-dimethylphenolate, and 2,6-di-tert-butylphenolate in dioxalane, dimethoxyethane, and pyridine has been investigated by a variety of methods including studies of vapor pressure barometry, **1**3C chemical shifts, **7Li nuclear quadrupole coupling constants, and **1**3C spin-lattice relaxation times. The phenolates with no ortho substituents from tetramers under most conditions. In pyridine at low concentrations and temperature the tetramers coexist with dimers. Lithium 2,6-dimethylphenolate forms dimers under all conditions studied, and lithium 2,6-di-tert-butylphenolate exists as a monomer or an oligomer depending on conditions. Attempts to establish solvation numbers for the aggregates from solvent **1**3C relaxation times have not been successful, and the reason for the failure, very fast solvent exchange, is discussed. The kinetics and thermodynamics of exchange between dimers and tetramers of lithium 3,5-dimentylphenolate in pyridine have been investigated, and the mechanism of interconversion is shown to involve additional solvation of the tetramer prior to dissociation.
- Jackman,DeBrosse
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p. 4177 - 4184
(2007/10/02)
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