- Highly enantioselective intramolecular cyclopropanation reactions of N-Allylic-N-methyldiazoacetamides catalyzed by chiral dirhodium(II) carboxamidates
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Catalytic diazo decomposition of representative N-allylic-N- methyldiazoacetamides produced the corresponding intramolecular cyclopropanation products in good to excellent yields and with exceptional enantiocontrol. In the simplest case, with N-allyl-N-methyldiazoacetamide, catalysis by dirhodium(II) tetrakis[methyl 2-oxapyrrolidine-5(S)-carboxylate], Rh 2(5(S)-MEPY)4, achieved the highest yield and enantioselectivity (93% ee). Dirhodium(II) tetrakis[methyl 2-oxo-1-(3- phenylpropanoyl) imidazolidin-4(S)-carboxylate], Rh2(4S)-MPPIM) 4, was preferred for substituted N-allylic-N-methyldiazoacetamides from which 92-95% ee's were obtained in intramolecular cyclopropanation reactions (88-95% yields), even when the catalyst was employed in only 0.1 mol %. Competition with intramolecular dipolar cycloaddition was minimized with the use of Nmethyldiazoacetamides relative to N-tert-butyldiazoacetamides.
- Doyle, Michael P.,Kalinin, Alexey V.
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- Isomerization and conformational transformations of the N-allyl-N-methylcarbamoyl bridging ligand in the (μ-H)Os3{μ-OCN(Me)CH2CH=CH2}(CO) 10 complex
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The (μ-H)Os3{μ-OCN(Me)CH2CH=CH2}(CO) 10 complex containing an allylic fragment in the N,N-dialkylsubstituted carbamoyl bridging ligand was synthesized. The stereochemical behavior of this complex in solution was investigated. As follows from the NMR spectral data, the complex undergoes reversible conformational (about the amide C-N bond) and irreversible allylic isomerization. Both conformers were isolated in the solid state by chromatography at a reduced temperature. The allylic isomerization occurs stereospecifically to produce the (μ-H)Os3{μ-OCN(Me)CH=CHMe}(CO)10 complex with the transoriented olefinic hydrogen atoms.
- Ershova,Maksakov,Golovin,Tkachev,Sheludyakova
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- Synthesis of Mixed Secondary and Tertiary Amines
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Abstract: A one-stage and facile method of synthesis of expensive methyl- and ethyl(allyl)amines, methyl- and ethyl(prop-2-ynyl)amines, and methyl- and ethyl(allyl)(3-phenylprop-2-ynyl)amines is developed. The synthesized amines present practical interest, because some (prop-2-ynyl)amines are used in the therapy cancer.
- Ayrapetyan, L. V.,Chukhajian, E. O.,Mkrtchyan, H. S.,Panosyan, H. A.
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p. 353 - 355
(2020/04/17)
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- A Modular Formal Total Synthesis of (±)-Cycloclavine
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Cycloclavine is a clavine-type Ergot alkaloid noteworthy for its unique pentacyclic skeleton featuring a 3-azabicyclo[3.1.0]hexane substructure. A short convergent route to the racemic alkaloid is described which comprises only eight linear steps and requires only four chromatographic purifications. The two key building blocks can be prepared in high yield from commercially available starting materials. Two consecutive coupling reactions, namely a selective alkylation of a dienolate and a Heck reaction, are the key steps of the reaction sequence. (Chemical Equation Presented).
- Netz, Natalie,Opatz, Till
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p. 1723 - 1730
(2016/03/01)
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- Synthesis and characterization of novel carbene complexes of phosphorus(V) fluorides with potential liquid-crystalline properties
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A series of novel push-push I and push-pull II carbene-stabilized complexes of phosphorus(V) fluorides bearing substituents with liquid-crystalline properties were synthesized by the oxidative addition of difluoroamines to phosphorus(III) halides. These octahedral complexes were characterized by NMR spectroscopy and X-ray analysis.
- Pajkert, Romana,B?ttcher, Tobias,Ponomarenko, Maksym,Bremer, Matthias,R?schenthaler, Gerd-Volker
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p. 8943 - 8951
(2013/09/23)
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- METHOD FOR TREATING CHRONIC PAIN USING MEK INHIBITORS
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The invention features a method for treating chronic pain using a compound selected from formulae (I), (II)A, (I)B and (I)C.
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- Analine derivatives as OSC inhibitors
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The present invention relates to compounds of formula (I) wherein U, Y, V, W, L, X, A1, A2, A3, A4, A5 and A6 are as defined in the description and claims and pharmaceutically acceptable salts and/or pharmaceutically acceptable esters thereof. The compounds are useful for the treatment and/or prophylaxis of diseases which are associated with 2,3-oxidosqualene-lanosterol cyclase such as hypercholesterolemia, hyperlipemia, arteriosclerosis, vascular diseases, mycoses, parasite infections, gallstones, tumors and/or hyperproliferative disorders, and/or treatment and/or prophylaxis of impaired glucose tolerance and diabetes.
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- 2,3-oxidosqualene-lanosterol cyclase inhibitors
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The present invention relates to piperidine derivatives useful for the treatment and/or prophylaxis of diseases which are associated with 2,3-oxidosqualene-lanosterol cyclase such as hypercholesterolemia, hyperlipemia, arteriosclerosis, vascular diseases, mycoses, gallstones, tumors and/or hyperproliferative disorders, and treatment and/or prophylaxis of impaired glucose tolerance and diabetes.
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- Benzenesulfonamide derivatives and their use as MEK inhibitors
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Benzenesulfonamides of formula (I), in which W is OR1, NR2OR1, NRARB, NR2NRARB, or NR2(CH2)2-4NRARBand the other variables as defined in the claims, are inhibitors of MEK and are effective in the treatment of proliferative diseases, cancer, stroke, heart failure, xenograft rejection, arthritis, cystic fibrosis, hepatomegaly, cardiomegaly, Alzheimer's disease, complications of diabetes, septic shock, and viral infection.
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- PHOSPHONIUM DIAZA-DIYLIDS AND AZA-YLDIID AS NEW AND EFFICIENT REAGENTS FOR PRIMARY AND SECONDARY AMINES SYNTHESIS
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Metallated aminophosphonium ylids, diaza-diylids and aza-yldiid, are investigated as reagents for primary and secondary amines synthesis.
- Cristau, Henri-Jean,Garcia, Chantal,Kadoura, Jumah,Torreilles, Eliane
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p. 151 - 154
(2007/10/02)
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- A NEW METHOD FOR EVALUATING THE STERIC HINDRANCE BY SUBSTITUENT
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New steric parameter, Οs, evaluating the steric hindrance around the reaction center was defined on the basis of molecular mechanics.
- Komatsuzaki, Tamiki,Sakakibara, Kazuhisa,Hirota, Minoru
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p. 3309 - 3312
(2007/10/02)
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- Thermal Oxidative Deamination of Aliphatic Amines to Aldehydes with Bis(diphenylphosphinyl) Peroxide
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Reaction of N-substituted alkylamines having pseudoacidic hydrogen at the 1-methylene group with bis(diphenylphosphinyl) peroxide yields the deaminated products by thermal elimination of diphenylphosphinic acid from the intermediate O-diphenylphosphinylhydroxylamines.
- Masse, Guy,Sturtz, Georges
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p. 907 - 910
(2007/10/02)
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- 5-Phenyl-2,4-pentadien-1-amines and method for inhibiting prostaglandin dehydrogenase
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5-Phenyl-2,4-pentadien-1-amines and salts thereof are provided having the structure STR1 wherein R1 is hydrogen, lower alkyl, lower alkoxy, hydroxy, lower alkanoyloxy, nitro, cyano, amino, carboxy or lower alkoxycarbonyl, and R2 and R3 are the same or different and are hydrogen, lower alkyl, alkenyl-lower alkyl, aralkyl, and substituted lower alkyl. These compounds possess useful pharmceutical activites due to their ability to inhibit the prostaglandin-inactivating enzyme 15-α-hydroxyprostaglandin dehydrogenase.
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