- Palladium-Catalyzed C-CN activation for intramolecular cyanoesterification of alkynes
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Conditions for the C-CN activation and intramolecular cyanoesterification of alkynes to provide butenolides in good to excellent yields are presented. Pd catalysts, high temperatures/short reaction times (microwave irradiation), and Lewis basic solvents m
- Rondla, Naveen R.,Levi, Samuel M.,Ryss, Jonathan M.,Berg, Rachel A. Vanden,Douglas, Christopher J.
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supporting information; experimental part
p. 1940 - 1943
(2011/06/17)
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- Synthesis of 3,3-disubstituted oxindoles through Pd-catalyzed intramolecular cyanoamidation
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The cyanoamidation of olefins was achieved. When N-(2-vinylphenyl)cyanoformamides were treated with palladium catalyst, intramolecular cyanoamidation took place to give corresponding 3,3-disubstituted oxindoles. P(t-Bu)3 showed a remarkable eff
- Yasui, Yoshizumi,Kamisaki, Haruhi,Ishida, Takayuki,Takemoto, Yoshiji
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supporting information; experimental part
p. 1980 - 1989
(2010/04/24)
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- Highly enantioselective intramolecular cyanoamidation: (+)-horsfiline, (-)-coerulescine, and (-)-esermethole
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(Figure Presented) The first asymmetric cyanoamidation with synthetically useful enantioselectivlty (ee up to 99%) to produce 3,3-disubstltuted oxindoles Is reported. Palladium catalysts with chi ral phosphoramldite ligands activate the cyanoformamide C-CN bond, which is subsequently functionalized with a tethered alkene to give all-carbon quaternary stereocenters. The use of the N,N-(i-Pr)2 derivative of octahydro-MonoPhos allowed the production of oxindoles with high enantioselectivlties. Cyanoformamides bearing free N-H groups are now tolerated, potentially allowing protecting-group-free synthesis. Oxindole products of cyanoamidation are rapidly transformed into (+)-horsfiline, (-)-coerulescine, and (-)-esermethole.
- Reddy, Venkata Jaganmohan,Douglas, Christopher J.
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supporting information; experimental part
p. 952 - 955
(2010/06/15)
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- Catalytic C-CN activation and asymmetric cyanoamidation of alkenes: Total syntheses of (+)-horsfiline, (-)-coerulescine, and (-)-esermethole
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The detailed study of Pd-catalyzed asymmetric cyanoamidation is reported. Excellent enantioselectivities are attributed to a chiral phosphosphoramidite ligand synthesized in one step from the commercially available materials. Cyanoamidation substrates are easy to prepare from the corresponding anilines. The 3,3-disubstituted oxindole products bear all-carbon quaternary stereocenters and contain a nitrile and an amide, which are valuable functional handles for the synthesis of many indole-containing natural products. Cyanoamidation tolerates free N-H groups, as demonstrated by the successful use of cyanoamidation in the syntheses of (+)-horsfiline and (-)-coerulescine.
- Reddy, Venkata Jaganmohan,Douglas, Christopher J.
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experimental part
p. 4719 - 4729
(2010/08/06)
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- Enantioselective synthesis of 3,3-disubstituted oxindoles through pd-catalyzed cyanoamidation
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(Chemical Equation Presented) The first enantioselective cyanoamidation of olefins provides quick access to a variety of 3,3-disubstituted oxindoles. The combination of Pd(dba)2, an optically active phosphoramidite, and N,N-dimethylpropylene urea (DMPU) i
- Yasui, Yoshizumi,Kamisaki, Haruhi,Takemoto, Yoshiji
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supporting information; experimental part
p. 3303 - 3306
(2009/05/07)
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- P38 MAP kinase inhibitors
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The present invention relates to compounds of Formula (I) that are p-38 MAP kinase inhibitors, pharmaceutical compositions containing them, methods for their use, and methods for preparing these compounds.
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- The photodissociation of carbonyl cyanide CO(CN)2 at 193 nm studied by photofragment translational energy spectroscopy
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The photodissociation of carbonyl cyanide CO(CN)2 at 193 nm was investigated by photofragment translational energy spectroscopy. For all the fragments created (CO, CN, OCCN, NCCN), the kinetic energy distributions were measured and two decay channels identified. The radical decay, CO(CN)2 + hν→OCCN+CN, dominates with a yield of 94%±2% and shows the available energy mainly (82%) channeled into the internal degrees of freedom of the fragments. A fraction of 18%±6% of the nascent OCCN radicals has sufficient energy to spontaneously decay to CO+CN involving a barrier ≤160 kJ/mol. With a yield of 6%±2% the molecular decay produces the fragments CO+NCCN. These fragments acquire a high available energy owing to the formation of the new C-C bond in NCCN. An average fraction of 70% is partitioned into internal fragment energy. Even the fastest fragments are still internally hot, indicating that with the high barrier expected, a substantial exit channel interaction is operative. The isotropic recoil distribution found for the products CN, OCCN, and NCCN further suggests that both the radical and the molecular decay are, on the time scale of a parent rotation, slow and probably indirect.
- Scheld, Heiner A.,Furlan, Alan,Huber, J. Robert
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p. 923 - 930
(2007/10/03)
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- Carbonyl cyanide O-oxide, the adduct of dicyanomethylene and dioxygen in argon matrices at 12 K
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Photolysis of dicyanodiazomethane in Ar matrices has been studied.Dicyanomethylene appears to be the sole product in dilute matrices, and its UV absorption spectrum and a revised IR spectrum are reported.In O2-doped Ar matrices, dicyanomethylene reacts with O2 to give carbonyl cyanide O-oxide as a very photolabile adduct.Four IR bands and a broad UV absorption at 375 nm are assigned to this species.On further photolysis, the carbonyl oxide rapidly decomposes to give carbonyl cyanide, by O-atom expulsion.A strong product absorption at 585 nm is assigned to a charge-transfer complex involving the expelled oxygen, but the precise nature of this species remains unknown.
- Dunkin, I. R.,McCluskey, A.
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p. 209 - 218
(2007/10/02)
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- Heterocycles from α-Nitroolefins, VIII. - 2-Methyl-3-pyrrolecarboxylates from α-Nitroolefins and Acetoacetates
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3-Pyrrolecarboxylates 4 can be prepared from α-nitroolefins 1 and acetoacetates 2 by two methods: (a) 1 and 2 react to give 4,5-dihydro-5-methyleneamino-3-furancarboxylates 3 which are hydrolyzed, (b) the nitronic acids 8, adducts of 1 and 2, yield with different reduction agents the heterocycles 4.
- Boberg, Friedrich,Garburg, Karl-Heinz,Goerlich, Karl-Joachim,Pipereit, Eberhard,Ruhr, Maria
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p. 239 - 250
(2007/10/02)
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