17197-84-1Relevant articles and documents
Aldosterone Synthase Inhibitor
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Page/Page column 8, (2013/02/27)
The present invention provides aldosterone synthase inhibitors of the formula: intermediates, methods for their preparation, pharmaceutical preparations, and methods for their use.
Generation and cycloaddition behavior of spirocyclic carbonyl ylides. Application to the synthesis of the pterosin family of sesquiterpenes
Padwa, Albert,Curtis, Erin A.,Sandanayaka, Vincent P.
, p. 73 - 81 (2007/10/03)
The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMC considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.
A novel one-flask cyclopentannulation involving a dilithiomethane equivalent as a β-connector of two enones. A highly efficient total synthesis of (±)-hirsutene
Cohen,McNamara,Kuzemko,Ramig,Landi Jr.,Dong
, p. 7931 - 7942 (2007/10/02)
Five- and six-membered rings can be constructed in one flask from two different enones and tris(phenylthio)methyllithium. The latter behaves as a dilithiomethane equivalent when its central carbon atom adds in conjugate fashion to one enone, becomes nucleophilic again when one of its phenylthio groups is exchanged for lithium in the presence of sec-butyllithium, and then undergoes conjugate addition to a second enone to provide a dienolate dianion. The latter can be oxidized to a 1,4-diketone incorporating a cyclopentane ring or induced to undergo an aldol reaction to produce a six-membered ring. In some of the cases, an interesting stereochemical equilibration occurs during the oxidation leading to one of two possible diastereomers and the overall process results in a highly efficient, stereospecific synthesis of (±)-hirsutene 13.
Cyclocarbonylation of acyclic 1,3-dienes via their tricarbonyl iron complexes: Cyclopenten-2-ones and dicarbonyl cyclopentadienyl iron halides
Franck-Neumann,Michelotti,Simler,Vernier
, p. 7361 - 7364 (2007/10/02)
Tricarbonyl iron complexes of acyclic 1,3-dienes can be converted to conjugated cyclopentenones by decomplexation with aluminium halides. Most complexes of simple dienes need drastic conditions for the cyclocarbonylation to occur (100 Atm CO, 100°C), with the exception of 1,1,3-trialkylbutadiene complexes which are nearly quantitatively converted into cyclopentenones at room temperature, even in the absence of a CO atmosphere. Under the same mild conditions, the other complexes lead in modest yields to cyclopentadienyl dicarbonyl iron halides by a cyclocarbonylation reaction followed by an aluminium halide promoted deoxygenation.
INTRAMOLECULAR ACYLATION OF α-SULFINYL CARBANION: A NEW GENERAL ROUTE TO 5-SUBSTITUTED Δ2-CYCLOPENTENONES
Pohmakotr, Manat,Phinyocheep, Pranee
, p. 2249 - 2252 (2007/10/02)
A general method for the preparation of 5-substituted Δ2-cyclopentenones via the intramolecular acylation of α-sulfinyl carbanions has been demonstrated.
COPPER (I) CATALYSIS OF OLEFIN PHOTOREACTIONS -9. PHOTOBICYCLIZATION OF alpha -, beta -, AND gamma -ALKENYLALLYL ALCOHOLS.
Salomon,Coughlin,Ghosh,Zagorski
, p. 998 - 1007 (2007/10/14)
Cyclobutylcarbinyl alcohols of the bicyclo left bracket 3. 2. 0 right bracket heptane ring system are produced by UV irradiation of alpha -, beta -, and gamma -alkenylallyl alcohols in the presence of copper (I) trifluoromethanesulfonate (CuOTf). endo-2-Hydroxy epimers of bicyclo left bracket 3. 2. 0 right bracket heptan-2-ols are generated stereoselectively. This result as well as the effect of CuOTf on the **1H NMR spectrum of 4,4-dimethyl-1,6-heptadien-3-ol suggests that coordination of two C equals C bonds and the hydroxyl group with a single copper (I) is important. The derived bicyclo left bracket 3. 2. 0 right bracket heptan 2-ones fragment cleanly at 580 degree C to afford cyclopent-2-en-1-ones. Geometric isomerization competes with photobicyclization of (E)- and (Z)-octa-2,7-dien-1-ols.
Nucleophilic substitution of 5,5-dimethyl-2-cyclopentenyl derivatives. Lack of SN2' reaction
Kopecky, Karl R.,Levine, Cyril
, p. 3273 - 3279 (2007/10/02)
Treatment of tetramethyl-1,3-cyclobutadienone with two equivalents of allyl oxide anion at 140 deg C yields 2,2-dimethyl-4-pentenoic acid which is cyclized via the acid chloride whith aluminium chloride to 5,5-dimethyl-2-cyclopentenone 4.Reduction of 4 with aluminium hydride provides 5,5-dimethyl-2-cyclopentenol 1-OH which is pyrolyzed to 5,5-dimethyl-1,3-cyclopentadiene in dimethylsulfoxide.Reduction of 4 with tri-t-butoxyaluminium hydride at -70 deg C gives 2,2-dimethylcyclopentanone.The 2,6-dichlorobenzoate ester of 1-OH failed to yield SN2' products under a variety of conditions.The rate constants for solvolysis of the p-nitrobenzoate esters of 1-OH, 2-cyclopentenol and Z-2-methyl-4-hexene-3-ol in 80 percent ethanol at 80 deg C are 20.2, 523, and 0.63 x 1E-6s-1, respectively, and the main products of solvolysis are 5-ethoxy-3,3-dimethylcyclopentene, 3-ethoxycyclopentene, and E-2-ethoxy-5-methyl-3-hexene, respectively.There is steric hindrance to solvatation during ionization of the p-nitrobenzoate of 1-OH.
