- Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
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A mild, reagent-cyanide-free, and efficient synthesis of O-phosphinoyl-protected cyanohydrins from readily available α-substituted malononitriles was realized using diarylphosphine oxides in the presence of O2. Mechanistic studies indicated that in addition to the initial aerobic oxidation of the malononitrile derivative notable features of this process include the formation of a tetrahedral intermediate and a subsequent intramolecular rearrangement. The phosphinoyl-protecting group can be removed by alcoholysis or by reduction with DIBAL-H.
- Zhang, Dapeng,Lian, Mingming,Liu, Jia,Tang, Shukun,Liu, Guangzhi,Ma, Cunfei,Meng, Qingwei,Peng, Haisheng,Zhu, Daling
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p. 2597 - 2601
(2019/04/17)
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- Titanium(III)-Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non-Free-Radical Mechanism
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A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C?C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6-collidine hydrochloride is investigated.
- Weweler, Jens,Younas, Sara L.,Streuff, Jan
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supporting information
p. 17700 - 17703
(2019/11/13)
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- Effect of Substituents on the Bond Strength of Air-Stable Dicyanomethyl Radical Thermochromes
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A series of substituted aryl dicyanomethyl radicals were synthesized, and the bonding thermodynamic parameters for self-dimerization were determined from van't Hoff plots obtained from variable-temperature electron paramagnetic resonance and ultraviolet-v
- Peterson, Joshua P.,Geraskina, Margarita R.,Zhang, Rui,Winter, Arthur H.
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p. 6497 - 6501
(2017/06/23)
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- Synthesis of substituted isoquinolines via Pd-catalyzed cross-coupling approaches
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Palladium complexes incorporating ligands based on a 1,3,5,7-tetramethyl-2, 4,8-trioxa-6-phosphaadamantanyl scaffold were used to catalyze the arylation of ethyl cyanoacetate, malononitrile, and various ketones. The products from these reactions can be el
- Todorovic, Nick,Awuah, Emelia,Albu, Silvia,Ozimok, Cory,Capretta, Alfredo
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supporting information; experimental part
p. 6180 - 6183
(2012/01/03)
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- A convenient protocol for the synthesis of hindered aryl malononitriles
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A technically feasible method has been developed for the synthesis of variety of aryl malononitriles in high yields (70-95%) using the palladium-catalyzed coupling reaction of malononitrile with aryl bromides and chlorides, respectively. The influence a s
- Schnyder, Anita,Indolese, Adriano F.,Maetzke, Thomas,Wenger, Jean,Blaser, Hans-Ulrich
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p. 3167 - 3169
(2008/02/13)
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- Single enantiomer, chiral donor-acceptor metal complexes from bisoxazoline pseudoracemates
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Single enantiomer, chiral donor-acceptor metal complexes were synthesized via the self-discriminating zinc(II) complexation of a pseudoracemic mixture of donor/acceptor-substituted bisoxazoline derivatives.
- Atkins, Jeffery M.,Moteki, Shin A.,DiMagno, Stephen G.,Takacs, James M.
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p. 2759 - 2762
(2007/10/03)
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- An efficient and mild CuI/L-proline-catalyzed arylation of acetylacetone or ethyl cyanoacetate
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The coupling reaction of aryl iodides with acetylacetone or ethyl cyanoacetate under catalysis of CuI/L-proline works at relatively mild conditions to provide 3-aryl-2, 4-pentanediones and α-aryl cyanoacetates in moderate to good yields. Georg Thieme Verlag Stuttgart.
- Jiang, Yongwen,Wu, Nan,Wu, Haihong,He, Mingyuan
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p. 2731 - 2734
(2007/10/03)
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- Industrial R&D on catalytic C-C and C-N coupling reactions: A personal account on goals, approaches and results
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R&D issues for the application of Pd- and Ni-catalyzed C-C and C-N coupling reactions in the fine chemicals industry are discussed. In a first part, some background is given on industrial R&D and the role of C-C and C-N coupling for preparative applicatio
- Blaser, Hans-Ulrich,Indolese, Adriano,Naud, Frederic,Nettekoven, Ulrike,Schnyder, Anita
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p. 1583 - 1598
(2007/10/03)
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- A convenient and efficient palladium-catalyzed system for cross-coupling of aryl bromides with active methylene compounds
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A simply catalytic system containing palladium-phosphine complex, generated in situ from PdCl2/tert-phosphino ligand in pyridine, has been systematically studied in the cross-coupling of bromobenzene with malononitrile or ethyl cyanoacetate anion. The effect of molar ratio of phosphine ligand to PdCl2 on the activity of the coupling was also discussed. It is found that the catalytic system has highly catalytic activity to produce aryl malononitriles and cyanoacetates in considerable yields (67-90%) when the substituted aryl bromides were used as substrates.
- Gao, Chengwei,Tao, Xiaochun,Qian, Yanlong,Huang, Jiling
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p. 1716 - 1718
(2007/10/03)
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- A highly efficient catalytic system for cross-coupling of aryl chlorides and bromides with malononitrile anion by palladium carbene complexes
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Six imidazolium chlorides (1-6) as precursors of 1,3-diaryl substituted N-heterocyclic carbene ligands were synthesized and evaluated in palladium-catalyzed cross-coupling reactions of aryl chlorides and bromides with malononitrile in the presence of NaH.
- Gao, Chengwei,Tao, Xiaochun,Qian, Yanlong,Huang, Jiling
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p. 1444 - 1445
(2007/10/03)
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- Estrogen receptor-β potency-selective ligands: Structure-activity relationship studies of diarylpropionitriles and their acetylene and polar analogues
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Through an effort to develop novel ligands that have subtype selectivity for the estrogen receptors alpha (ERα) and beta (ERβ), we have found that 2,3-bis(hydroxyphenyl)propionitrile (DPN) acts as an agonist on both ER subtypes, but has a 70-fold higher relative binding affinity and 170-fold higher relative potency in transcription assays with ERβ than with ERα. To investigate the ERβ affinity- and potency-selective character of this DPN further, we prepared a series of DPN analogues in which both the ligand core and the aromatic rings were modified by the repositioning of phenolic hydroxy groups and by the addition of alkyl substituents and nitrile groups. We also prepared other series of DPN analogues in which the nitrile functionality was replaced with acetylene groups or polar functions, to mimic the linear geometry or polarity of the nitrile, respectively. To varying degrees, all of the analogues show preferential binding affinity for ERβ (i.e., they are ERβ affinity-selective), and many, but not all of them, are also more potent in activating transcription through ERβ than through ERα (i.e., they are ERβ potency-selective). meso-2,3-Bis(4-hydroxyphenyl)succinonitrile and dl-2,3-bis(4-hydroxyphenyl)succinonitrile are among the highest ERβ affinity-selective ligands, and they have an ERβ potency selectivity that is equivalent to that of DPN. The acetylene analogues have higher binding affinities but somewhat lower selectivities than their nitrile counterparts. The polar analogues have lower affinities, and only the fluorinated polar analogues have substantial affinity selectivities. This study suggests that, in this series of ligands, the nitrile functionality is critical to ERβ selectivity because it provides the optimal combination of linear geometry and polarity. Furthermore, the addition of a second nitrile group β to the nitrile in DPN or the addition of a methyl substitutent at an ortho position on the β-aromatic ring increases the affinity and selectivity of these compounds for ERβ. These ERβ-selective compounds may prove to be valuable tools in understanding the differences in structure and biological function of ERα and ERβ.
- Meyers,Sun,Carlson,Marriner,Katzenellenbogen,Katzenellenbogen
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p. 4230 - 4251
(2007/10/03)
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- 3-[5-substituted benzyl)amino]-2-phenylpiperidines as substance P antagonists
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This invention provides a compound of the formula: STR1 and its pharmaceutically acceptable salts, wherein R 1 is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, halo C 1 -C 6 alkyl or terahydropyranyl, having one or more substituents selected from cyano, 1,3-thiazolanyl, COOR 2, COR 2, OCOR 2, CONR 3 R 4, NR 3 R 4, NR 5 COR 3 and C.ident.CR 6, wherein R 2 is hydrogen or C 1 -C 4 alkyl, R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, R 5 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl and R 6 is hydrogen, halo, cyano, C 1 -C 6 alkyl, COOH, COO(C 1 -C 4 alkyl) or phenyl; X is C 1 -C 6 alkoxy or halo C 1 -C 6 alkoxy; and Ar is phenyl optionally substituted with halo.These compounds are useful in the treatment of allergic disorders, angiogenesis, gastrointestinal disorders, central nervous system disorders, inflammatory diseases, emesis, urinary incontinence, pain, migraine, sunburn, and diseases, disorders and adverse conditions caused by Helicobacter pylori, in a mammalian subject.
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- The Benzene Ring as a Dipolarophile: Reactions of Monosubstituted Benzenes with Tetracyanoethylene Oxide
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The reaction of tetracyanoethylene oxide on one hand and toluene, chlorobenzene, fluorobenzene, anisole, and nitrobenzene, on the other, has been studied.Toluene and the halogenobenzenes yield mixtures of monoadducts, anisole yield p-methoxyphenylmalononitrile and its dimer and nitrobenzene does not react.These results are discussed with the help of a qualitative orbital model. 1H-NMR analysis of some monoadducts has been carried out.Keywords: Benzene derivatives; Tetracyanoethylene oxide; 1,3-Dipolar cycloaddition.
- Hoz, A. de la,Pardo, C.,Elguero, J.,Jimeno, M. L.
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- A NEW APPROACH TO ARYLMALONONITRILES
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Arylmalononitriles were prepared from the corresponding benzoyl chlorides by three reaction steps.Treatment of the starting substances with cyanotrimethylsilane in the presence of pyridine gave dicyanotrimethylsiloxymethylbenzenes, which were transformed
- Yamaguchi, Shunro,Araki, Hisashi,Hanafusa, Terukiyo
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p. 685 - 688
(2007/10/02)
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- A New Method of Synthesis of Arylmalononitriles catalysed by a Palladium Complex
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Arylmalononitriles are prepared in good yields using a palladium-catalysed coupling reaction between aryl halides and malononitrile.
- Uno, Mitsunari,Seto, Koji,Takahashi, Shigetoshi
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p. 932 - 933
(2007/10/02)
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