Synthesis of bifunctional 2-aminodmap/prolinamide organocatalysts and their use in asymmetric michael reaction to afford warfarin

Download

index.pdf

Date

2012

Author

Akkoca, Hasan Ufuk

Metadata

Show full item record

Item Usage Stats

102
views

14
downloads

In the first part of this thesis, the construction of the novel bifunctional proline-(1R,2R)-2-aminoDMAP organocatalyst backbone is described. Target compound has both Lewis base and Brønsted acid catalaphoric sites. The Lewis base site is synthesized via selective mono-N-pyridilization of trans-(1R,2R)-cyclohexane-1,2-diamine by Cu catalysis and Brønsted acid site is subsequently introduced by anchoring L-proline unit. In the second part, catalytic activities of organocatalysts are tested in asymmetric Michael addition reaction between a cyclic 1,3-dicarbonyl compound 4-hydroxycoumarin and various α,β-unsaturated ketones to afford optically active warfarin as anticoagulants, in one step. Reaction parameters such as solvent, temperature, equivalency, and cocatalyst were screened. Enantiomeric excess value (ee) up to 72% is attained.

Subject Keywords

Chemistry, Organic

URI

http://etd.lib.metu.edu.tr/upload/12613984/index.pdf
https://hdl.handle.net/11511/21001

Collections

Graduate School of Natural and Applied Sciences, Thesis

Suggestions

OpenMETU
Core

Synthesis of 1,4-Thiazepines Kelgokmen, Yılmaz; Zora, Metin (American Chemical Society (ACS), 2018-08-03) An efficient, general, and unprecedented methodology for the synthesis of 2-methylene-2,3-dihydro-1,4-thiazepines from N-propargylic beta-enaminones is described. Initially, N-propargylic beta-enaminones were thionated with Lawesson's reagent in good to high yields, and then the resulting N-propargylic beta-enaminothiones were subjected to electrophilic cyclization. When treated with zinc chloride in refluxing chloroform, Npropargylic beta-enaminothiones underwent electrophilic cyclization to yield 2-methyl...
Synthesis of new ferrocenyl-substituted aziridines via the Gabriel-Cromwell reaction Doğan, Özdemir; BULUT, ADNAN (Informa UK Limited, 2005-01-01) The Gabriel -Cromwell method is applied successfully in the synthesis of ferrocenyl-substituted aziridines. Acryloyl- and crotonoy1ferrocenes are brominated first and then reacted with benzylamine, diisopropylamine, and furfurylamine in the presence of triethylamine. The aziridines are obtained in more than 90% isolated yields.
Synthesis of 3-[(4-Nitrophenyl)thio]-Substituted 4-Methylene-1-pyrrolines from N-Propargylic beta-Enaminones Korkmaz, Esra; Zora, Metin (American Chemical Society (ACS), 2020-04-03) A facile and efficient method for the synthesis of 3-[(4-nitrophenyl)thio]-substituted 4-methylene-1-pyrrolines is described. When treated with 4-nitrobenzenesulfenyl chloride in refluxing acetonitrile, N-propargylic beta-enaminones produced alpha-sulfenylated N-propargylic beta-enaminones, which, in the presence of sodium hydride or cesium carbonate, underwent nucleophilic cyclization to afford 4-methylene-3-[(4-nitrophenyl)thio]-1-pyrrolines in good to high yields. It was shown for the first time that on ...
Synthesis and enzymatic resolution of various cyclopentenoid and cyclohexenoid type compounds İyigün, Çiğdem; Tanyeli, Cihangir; Department of Chemistry (2005) The aim of this thesis is to synthesize enantiomerically enriched cyclopentenoid and cyclohexenoid type of compounds with quaternary carbon stereocenters that are the simplest precursors of the complex natural products. The first part of the study involves the preparation of ?'-acetoxy ?'-substituted ?,β-unsaturated cyclic ketones. Methylation, ethylation, benzylation and allylation of cyclohexenone and cyclopentenone derivatives are performed. Then, these compounds are regioselectively oxidized at the ?'-p...
Synthesis and reactions of alpha-keto-beta-hydroxyphosphonates Barış, Şehriban; Demir, Ayhan Sıtkı; Department of Chemistry (2007) This thesis presents synthesis and different reactions of alpha-keto-beta-hydroxyphosphonates. Toward this aim, the hydroxyl functionality of alpha-hydroxycarboxylic acids were protected with alkyl or acyl groups and then formation of acid chloride followed by the reaction with trialkylphosphite furnished protected alpha-keto-beta-hydroxyphosponates. Nucleophilic addition reactions were applied to these compounds to obtain quaternary alcohols with phosphonate functionality. The addition reactions were tried...

Citation Formats

H. U. Akkoca, “Synthesis of bifunctional 2-aminodmap/prolinamide organocatalysts and their use in asymmetric michael reaction to afford warfarin,” M.S. - Master of Science, Middle East Technical University, 2012.