Synthesis of (3,6-dihydro-2H-pyran-2-yl)phosphonate derivatives and investigation of catalyst effect on frontier molecular orbitals using DFT method

Hossain, Md Shakhawoat
Ozpinar, Gul Altinbas
Nadeem, Said
Demir, Ayhan Sıtkı
Hetero Diels-Alder (HDA) reactions between 2,3-dimethyl-1,3-butadiene and diethyl ester of aroyl phosphonates catalyzed by AlCl3 to afford (3,6-dihydro-2H-pyran-2-yl) phosphonate derivatives were investigated. Aroyl phosphonates with electron-withdrawing groups generally resulted in better isolated chemical yields. A stoichiometric amount of AlCl3 rather than a catalytic amount was necessary to activate the cycloaddition reaction. The amount of AlCl3 catalyst and its effect on LUMO of ethyl ester benzoyl phosphonate were also investigated by performing density functional theory (DFT) (B97D/6-31+G(d,p)) computations in dichloromethane. An increased loading of AlCl3 induced a considerable decrease in the LUMO energy of ethyl ester of benzoyl phosphonate. The computed Gibbs free activation energy is 17.03kcal/mol in DCM at 0 degrees C using the same computational level.


Synthesis of beta-chloro-alpha-aminophosphonate derivatives via the regioselective ring opening of unactivated aziridine-2-phosphonates
Polat-Cakir, Sidika; BEKSULTANOVA, Nurzhan; Doğan, Özdemir (Informa UK Limited, 2018-12-02)
A series of unactivated racemic and chiral aziridine-2-phosphonates were synthesized by modified Gabriel-Cromwell reaction. Ring opening reaction of the synthesized phosphonates by gaseous HCl provided access to a wide range of biologically interesting novel beta-chloro-alpha-aminophosphonates. All reactions toward each of the above-mentioned products can be conducted regioselectively in high yields.
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Kayalar, Metin; Demir, Ayhan Sıtkı; Department of Chemistry (2005)
A convenient and new method for the synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives starting from 1,3,-dicarbonyl compounds through acid catalyzed cyclization reaction is described. Alkylation of 1,3-dicarbonyl compound with propargyl bromide followed by one step cyclization with the introduction of primary amines in the presence of catalytic amount of triflouroacetic acid (TFA) affords the corresponding pyrrole derivatives in high yields. The investigations on the studies of developing a new meth...
Synthesis of 2-heteroaryl substituted chiral fused cyclopenta[c]pyridine derivatives via pauson-khand reaction
Gümrükçü, Yasemin; Tanyeli, Cihangir; Department of Chemistry (2009)
The racemic homoallylic and homopropargylic alcohol derivatives were resolved by applying chemoenzymatic method using various lipase type enzymes i.e., PS-C II, Lipozyme, CAL-B. The enantiomeric excess values of the resultant alcohols were determined by HPLC. These enantiomerically enriched homoallylic and homopropargylic alcohols were subjected to N-propargylation and N-allylation, respectively, by SN2 and modified Mitsunobu reactions. During the course of all reactions, stereochemistry of the chiral cente...
Synthesis of ferrocenyl quinolines
Zora, Metin (Elsevier BV, 2008-06-01)
A convenient one-pot synthesis of ferrocenyl-substituted quinolines via a molecular iodine-catalyzed reaction of ferrocenylimines with enolizable aldehydes is reported. First, nucleophilic addition of the in situ generated enol to ferrocenylimine produces beta-anilinopropionaldehyde, which then undergoes intramolecular Friedel-Crafts reaction to give dihydroquinoline derivative. Finally, subsequent dehydration and aerobic oxidation affords ferrocenyl quinolines.
Synthesis of Ferrocenyl Substituted Aziridines
Zeytinci, Serhat; Doğan, Özdemir; Department of Chemistry (2006)
Immobilization of tyrosinase enzyme was performed in the matrices obtained via copolymerization of terephthalic acid bis-(2-thiophen-3-yl ethyl) ester (TATE) with pyrrole. During electrochemical polymerization of pyrrole, enzyme molecules were entrapped in the copolymer matrice. Activity measurements were performed by using Besthorn̕s Hydrazone method which includes spectrophotometric analysis of quinones produced by the enzyme. Enzyme electrodes were characterized in terms of maximum reaction rate (Vmax) a...
Citation Formats
M. S. Hossain, S. POLAT ÇAKIR, G. A. Ozpinar, S. Nadeem, and A. S. Demir, “Synthesis of (3,6-dihydro-2H-pyran-2-yl)phosphonate derivatives and investigation of catalyst effect on frontier molecular orbitals using DFT method,” PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, pp. 1262–1267, 2016, Accessed: 00, 2020. [Online]. Available: