- High pressure organic chemistry; XI. A new convenient synthesis of aromatic amines from activated phenols
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Aryl triflates containing electron-withdrawing substituents efficiently react with amines in refluxing acetonitrile or at 10 kbar pressure to give various aromatic amines.
- Kotsuki,Kobayashi,Suenaga,Nishizawa
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Read Online
- First Study of the Thermal and Storage Stability of Arenediazonium Triflates Comparing to 4-Nitrobenzenediazonium Tosylate and Tetrafluoroborate by Calorimetric Methods
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Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography-mass spectrometry (MS) and liquid chromatography-MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.
- Bondarev, Alexander A.,Naumov, Evgeny V.,Kassanova, Assiya Zh.,Krasnokutskaya, Elena A.,Stankevich, Ksenia S.,Filimonov, Victor D.
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supporting information
p. 2405 - 2415
(2019/10/11)
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- DIBENZOOXEPIN DERIVATIVE
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A dibenzoxepin derivative represented by the following general formula (I) wherein Y is a hydrogen atom and the like, RA is a hydrogen atom and the like, X is the formula (b3) wherein RB is a hydrogen atom and the like, and the like,
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Paragraph 0386
(2014/06/24)
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- CHIRAL PHOSPHINES FOR PALLADIUM-CATALYZED ASYMMETRIC ALPHA-ARYLATION OF ESTER ENOLATES TO PRODUCE TERTIARY STEREOCENTERS IN HIGH ENANTIOSELECTIVITY
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The disclosure provides new and improved methods for the Pd-catalyzed asymmetric α-arylation of ester compounds, which produce the corresponding α-aryl moiety in high enantioselectivity (generally >90% ee). The present methods utilize a palladium catalyst supported by new (R)-H8-BINOL-derived monophosphine ligands. The method is applicable to a wide variety of aryl triflate substrates having variations in both electronic and steric properties. These aryl triflate substrates react with various α-alkyl (Z)- and/or (E)-0-trimethylsilyl ketene acetals in the presence of a Pd catalyst, (R)-H8-BINOL-derived monophosphine ligand, and a mild activator, for example, LiOAC, to provide the asymmetric α-arylation of ester compounds in high ee.
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Paragraph 00164-00165
(2013/03/26)
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- Intermolecular mizoroki-heck reaction of aliphatic olefins with high selectivity for substitution at the internal position
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New ligand for old reaction: The title reaction of aryltriflates with aliphatic olefins leads to substitution at the internal position with high selectivity. The ratio of the desired isomer (shown in the scheme) to the sum of all other isomers is generall
- Qin, Liena,Ren, Xinfeng,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
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supporting information; experimental part
p. 5915 - 5919
(2012/07/30)
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- Regioselectivity switch achieved in the palladium catalyzed α-arylation of enones by employing the modified Kuwajima-Urabe conditions
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A new regioselective approach to the synthesis of α-aryl enones is reported. This represents an important application of the Kuwajima-Urabe protocol toward the synthesis of this simple albeit complex functional array. Several α-aryl enones were synthesized by the palladium catalyzed arylation of triethylsilylenol ethers of enones with high regioselectivity and broad scope, utilizing sterically encumbered electron-rich phosphine ligands to drive the reaction.
- Kale, Ajit Prabhakar,Pawar, Govind Goroba,Kapur, Manmohan
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supporting information; experimental part
p. 1808 - 1811
(2012/06/18)
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- Synthesis of enantiomerically enriched 3-amino-2-oxindoles through a palladium-mediated asymmetric intramolecular arylation of α-ketimino amides
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A highly efficient and enantioselective synthesis of 3-amino-2-oxindoles through a palladium-catalyzed asymmetric intramolecular arylation of R-ketimino amides using (R)-DiFluorPhos as the coordinating ligand is reported. This report constitutes the first
- Tolstoy, Paeivi,Lee, Samantha X. Y.,Sparr, Christof,Ley, Steven V.
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supporting information
p. 4810 - 4813,4
(2012/12/12)
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- Synthesis of enantiomerically enriched 3-amino-2-oxindoles through a palladium-mediated asymmetric intramolecular arylation of α-ketimino amides
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A highly efficient and enantioselective synthesis of 3-amino-2-oxindoles through a palladium-catalyzed asymmetric intramolecular arylation of R-ketimino amides using (R)-DiFluorPhos as the coordinating ligand is reported. This report constitutes the first
- Tolstoy, P?ivi,Lee, Samantha X.Y.,Sparr, Christof,Ley, Steven V.
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supporting information
p. 4810 - 4813
(2013/01/15)
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- Palladium-catalyzed desulfitative arylation by C-O bond cleavage of aryl triflates with sodium arylsulfinates
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An efficient Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates as arylation reagents by C-O bond cleavage of aryl triflates was developed. With only 2 mol % of Pd(OAc)2 as catalyst and XPhos as ligand, the reaction proceeded well for a range of substrates.
- Zhou, Chao,Liu, Qingjiang,Li, Yaming,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10468 - 10472
(2013/01/15)
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- An enantioselective, intermolecular α-arylation of ester enolates to form tertiary stereocenters
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In transition-metal catalyzed, asymmetric α-arylation of carbonyl compounds, formation of tertiary centers with high enantioselectivity is a longstanding problem, due to easy enolization of the monoarylation products. Herein, we report such examples using a palladium catalyst supported by a new, (R)-H8-BINOL-derived monophosphine. Silyl ketene acetals, together with a weakly basic activator, were used as equivalents of ester anions, and they reacted smoothly with aryl triflates in excellent enantiomeric excess (ee). The usefulness of the reaction was demonstrated in a gram-scale synthesis of (S)-Naproxen in 92% ee.
- Huang, Zhiyan,Liu, Zheng,Zhou, Jianrong
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supporting information; experimental part
p. 15882 - 15885
(2011/11/13)
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- Non-steroidal dissociated glucocorticoid agonists: Indoles as A-ring mimetics and function-regulating pharmacophores
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We report a SAR of non-steroidal glucocorticoid mimetics that utilize indoles as A-ring mimetics. Detailed SAR is discussed with a focus on improving PR and MR selectivity, GR agonism, and in vitro dissociation profile. SAR analysis led to compound (R)-33 which showed high PR and MR selectivity, potent agonist activity, and reduced transactivation activity in the MMTV and aromatase assays. The compound is equipotent to prednisolone in the LPS-TNF model of inflammation. In mouse CIA, at 30 mg/kg compound (R)-33 inhibited disease progression with an efficacy similar to the 3 mg/kg dose of prednisolone.
- Betageri, Raj,Gilmore, Thomas,Kuzmich, Daniel,Kirrane, Thomas M.,Bentzien, J?rg,Wiedenmayer, Dieter,Bekkali, Younes,Regan, John,Berry, Angela,Latli, Bachir,Kukulka, Alison J.,Fadra, Tazmeen N.,Nelson, Richard M.,Goldrick, Susan,Zuvela-Jelaska, Ljiljana,Souza, Don,Pelletier, Josephine,Dinallo, Roger,Panzenbeck, Mark,Torcellini, Carol,Lee, Heewon,Pack, Edward,Harcken, Christian,Nabozny, Gerald,Thomson, David S.
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scheme or table
p. 6842 - 6851
(2011/12/22)
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- One-pot synthetic procedure for 2,2′-disubstituted biaryls via the Suzuki coupling reaction of aryl triflates in a biphasic solvent system
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A one-pot synthetic procedure for 2,2′-disubstituted biaryls was developed via a Suzuki cross-coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na2/
- Miura, Masanori,Koike, Takanori,Ishihara, Tsukasa,Hirayama, Fukushi,Sakamoto, Shuichi,Okada, Minoru,Ohta, Mitsuaki,Tsukamoto, Shin-Ichi
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p. 3809 - 3820
(2007/10/03)
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- O-nitrophenyltriflates in quinoline synthesis : Easy access to a streptonigrin synthon
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An efficient route to a wide range of 2-hydroxyquinolines from o-nitrophenyltriflates via a Heck reaction is reported, with emphasis on the preparation of a synthetic equivalent of the streptonigrin AB ring system.
- Holzapfel, Cedric W.,Dwyer, Catherine
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p. 215 - 219
(2007/10/03)
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- Stille and suzuki cross coupling reactions of o-nitrophenyl triflates: A versatile route to a variety of heterocycles
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The cross coupling reactions of selected o-nitrophenyl triflates with arylstannane and arylboron substrates are reported. The resultant 2-nitrobiphenyls provide ready access to a variety of substituted heterocycles.
- Holzapfel, Cedric W.,Dwyer, Catherine
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p. 1513 - 1518
(2007/10/03)
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- 4-Nitrophenyltriflate as a New Triflating Agent
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Aryl triflates were prepared under mild conditions using 4-nitrophenyl triflate (1) as a stable, crystalline triflating agent.
- Zhu, Jieping,Bigot, Antony,Elise, Marie,Dau, Tran Huu
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p. 1181 - 1182
(2007/10/03)
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- A Facile Preparation of Aryl Triflates. Decomposition of Arenediazonium Tetrafluoroborate Salts in Trifluoromethanesulfonic Acid
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The thermal or photochemical decomposition of arenediazonium tetrafluoroborate salts n trifluoromethanesulfonic acid, with or without organic bases such as pyridine, provides aryl triflates in high yields.
- Yoneda, Norihiko,Fukuhara, Tsuyoshi,Mizokami, Takao,Suzuki, Akira
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p. 459 - 460
(2007/10/02)
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