Search results for "cyclization"
showing 10 items of 114 documents
One-Pot Synthesis of Pyrrole-2-carboxylates and -carboxamides via an Electrocyclization/Oxidation Sequence
2014
An electrocyclic ring closure is the key step of an efficient one-pot method for the synthesis of pyrrole-2-carboxylates and -carboxamides from chalcones and glycine esters or amides. The 3,4-dihydro-2H-pyrrole intermediates generated in situ are oxidized to the corresponding pyrroles by stoichiometric oxidants or by catalytic copper(II) and air in moderate to high yields. A wide range of functional groups are tolerated, and further combination with an in situ bromination gives access to polyfunctional pyrrole scaffolds.
Synthesis of a bridgehead nitrogen system. Imidazo[1,5-b]pyridazine derivatives
1979
3,4-Dibenzoyl-2-oxobutyrate 4-semicarbazone (6a), ethyl 2,4-dioxo-3-phenacylvalerate 3-semicarbazone (6b) and diethyl phenacyloxalectate 3-semicarbazone (6c) via acid catalysed intramolecular cyclization afforded 2-phenyl-4-R-3H-imidazo[1,5-d]pyridazine-5,7-(6H)diones (8d,e,f). Elemental analyses and spectroscopic data (ir, nmr, ms) were in good agreement with the assigned structures.
Antiprotozoan lead discovery by aligning dry and wet screening: Prediction, synthesis, and biological assay of novel quinoxalinones
2014
Protozoan parasites have been one of the most significant public health problems for centuries and several human infections caused by them have massive global impact. Most of the current drugs used to treat these illnesses have been used for decades and have many limitations such as the emergence of drug resistance, severe side-effects, low-to-medium drug efficacy, administration routes, cost, etc. These drugs have been largely neglected as models for drug development because they are majorly used in countries with limited resources and as a consequence with scarce marketing possibilities. Nowadays, there is a pressing need to identify and develop new drug-based antiprotozoan therapies. In …
Ir-Catalyzed Cycloaddition of Tribenzocyclyne with Biphenylenes
2021
We demonstrate that Ir-catalyzed C-C bond activation in biphenylenes followed by a reaction with tribenzocyclyne is a suitable method for synthesizing strained and unknown monoadducts with the tetradehydrotetrabenzo[a,c,e,i]cyclododecene scaffold ([12]annulenes). Modification of reaction conditions also furnished [12]annulene products with cis and/or trans double bonds formed by hydrogen transfer. The [9]annulene side product was formed upon the reaction of the benzyl radical with tribenzocyclyne during the Bergman cyclization. All isolated compounds were fully characterized by HRMS, NMR, and X-ray diffraction analysis.
The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C16 -C25 Fragment
2005
The mechanism of the double intramolecular hetero-Michael addition, a key reaction in the planned synthesis of the natural product calyculin C, has been studied by NMR. The cyclization follows Baldwin’s rules and proceeds first through a six-membered ring closure (6-endo-dig), followed by a five-membered ring cyclization (5-exo-trig). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
A study of the mechanism of the oxidative cyclization of benzaldehyde semicarbazones induced by cupric perchlorate in acetonitrile
1995
Treatment of benzaldehyde semicarbazones 1a-i with cupric perchlorate in acetonitrile at 40 provided selectively the corresponding 1,2,4-triazolin-5-ones 2a-i. The relative rate constants for 2a-i formation were determined by the competitive method. The results obtained showed that electron-donating substituents (methyl and methoxy) increase the reaction rate, while the reverse was found for electron-withdrawing substituents (chloro and nitro group). The reactivity data are discussed on the grounds of two possible mechanisms.
CuCl catalyzed radical cyclisation of N-alpha-perchloroacyl-ketene-N,S-acetals: a new way to prepare disubstituted maleic anhydrides
2012
The discovery that cycloalkanes can form thermomorphic systems with typical polar organic solvents has led to the development of less-polar electrolyte solutions. Their mixing and separation can be regulated reversibly at a moderate temperature range. The phase switching temperature can be controlled by changing the solvent compositions. While biphasic conditions are maintained below the phase switching temperature, conductive monophasic conditions as less-polar electrolyte solutions are obtained above the phase switching temperature. After the electrochemical transformations, biphasic conditions are reconstructed below the phase switching temperature, facilitating the separation of cycloal…
Stereocontrolled approach to δ- and γ-lactones and 1,3-diols. The role of X− ion in the selenolactonization
2002
Abstract Two complementary approaches have been realized for the stereoselective synthesis of 4,6-disubstituted δ-lactones and 1,3- anti and syn diols. In the 6- endo selenolactonization the role of the X − ion on the stereoselectivity is shown. Moreover, the highly stereoselective transformation of the 6- endo δ-lactone to the 5- exo γ-lactone is reported.
Host−Guest Interactions between β-Cyclodextrin and the (Z)-Phenylhydrazone of 3-Benzoyl-5-phenyl-1,2,4-oxadiazole: The First Kinetic Study of a Ring…
2002
The effect of beta-cyclodextrin (beta-CD) on the mononuclear heterocyclic rearrangement of the (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) in aqueous borate buffer at pH = 9.6 has been analyzed at temperatures ranging from 293.15 to 313.15 K. The trend of the absorption spectra of 1 as a function of time has been accounted for with the formation of two different 1:1 complexes between beta-CD and 1, the first, "unreactive" complex being formed faster than the "reactive" one. The occurrence of negative activation enthalpy values for the studied interconversion evidences the kinetic relevance of inclusion processes. Computational models elaborated using the MM2 molecular mec…
Diastereoselective Intramolecular Additions of Allyl- and Propargylsilanes to Iminium Ions: Synthesis of Cyclic and Bicyclic Quaternary Amino Acids
2010
Chiral imino lactones derived from (R)-phenylglycinol containing an allyl- or propargyltrimethylsilyl group in the side chain readily cyclized in the presence of acidic reagents to afford spirocyclic compounds with high diastereoselectivity. Removal of the chiral auxiliary produced 2-substituted 1-aminocycloalkanecarboxylic acids, whereas further cyclizations by means of metathesis or hydroamination reactions led to bicyclic derivatives of pipecolic acid and proline.