Synthesis of cycloheptadiene annelated dihydrofurane derivatives and design of pyrrolo-pyrrolo-pyrazines and α-alkylidyn-γ-butyrolactones via alkyne cyclization /

Aslanoğlu, Furgan
Owing to fascinating regiochemistry and controversial reaction mechanism, the oxidative free radical cyclization reaction of unsaturated bicyclic endoperoxides is an interesting area. In the first part of the thesis, we reacted various 1,3-dicarbonyl compounds with cycloheptatriene in the presence of Ce(NH4)2(NO3)6 to obtain dihydrocyclohepta[b]furan derivatives. Then, the formed 1,3-cycloheptadiene unit of dihydrocyclohepta[b]furan derivatives was reacted with singlet oxygen to give the corresponding bicyclic endoperoxides. Bicyclic endoperoxides which include acetyl group were reacted with CoTPP, AuCl3 and NEt3. Dihydrocyclohepta[b]furan derivatives were oxidized with SeO2 to tropone derivatives, biologically interesting molecule. In the second part of the thesis, a new synthetic method for the synthesis of pyrrolo- pyrrolo-pyrazine derivatives was developed. Firstly, pyrrole was reacted with 2-pyrrolidinone to generate 2,2'-(1'-pyrrolinyl)pyrrole, which was reacted with propargyl bromide derivatives to afford propargylated compounds which were further derivatized via Sonogashira cross coupling reaction. Pd/C-supported cyclization reactionof propargylated compounds and their derivative with Pd/C, afforded pyrrolo-pyrrolo-pyrazine derivatives. In the last part of the thesis, we examined the reaction of bicyclic endoperoxides with gold salt for the first time. Firstly, we synthesized bicyclic endoperoxide, 2,3-dioxabicyclo[2.2.2]oct-5-ene by the reaction of cyclohexa-1,3-diene with singlet oxygen. Reaction of unsaturated bicyclic endoperoxide with alkynes in the presence of Au(L)/AgOTf resulted in the formation of α-alkylidine-γ-butyrolacton derivatives.


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Bengu, B; Toppare, Levent Kamil; Kalaycioglu, E (2001-01-01)
2-(N-pyrrolyl)ethylvinyl ether (2-NEVE) was synthesized from 2-chloroethylvinyl ether (2-CEVE) via a phase catalysis reaction. Cyclic voltammetric studies were carried out to check for the electroactivity of 2-NEVE. Poly(2-(N-pyrrolyl)ethylvinyl ether) [poly(2-NEVE)] was synthesized via chemical methods. Graft copolymers of pyrrole and 2-NEVE were synthesized by electrochemical methods. The chemical structures of 2-NEVE and poly(2-NEVE) were investigated by several spectroscopic methods. Graft copolymers we...
Synthesis and characterization of conducting copolymers of succinic acid bis-(4-pyrrol-1-yl-phenyl) ester and their electrochromic properties
Ertas, M; Çırpan, Ali; Toppare, Levent Kamil (Elsevier BV, 2004-05-07)
A new dipyrrolyl monomer was synthesized via the reaction between 4-pyrrol-1-yl phenol and butanedioyl dichloride. Electrochemical behavior of this monomer, succinic acid bis-(4-pyrrol-1-yl-phenyl) ester (SM) was studied. Homopolymerization was achieved by chemical and constant Current electrolysis methods. Copolymerization of SM with thiophene was performed by constant potential electrolysis in acetonitrile (AN)-tetrabutylammonium tetrafluoroborate (TBAFB) and dichloromethane (DCM)-TBAFB, solvent-electroly...
Synthesis of a bipyridine-derived achiral thiourea trifluoromethanesulfonic acid salt and its application as an additive in organocatalytic asymmetric reactions
Demir, Ayhan Sıtkı; BAŞÇEKEN, SİNAN (2013-10-16)
The host-guest complex of a proline-thiourea bipyridine trifluoromethanesulfonic acid salt can catalyze organocatalytic asymmetric reactions such as aldol, Michael, and Mannich in polar protic medium with high stereoselectivities. The privileged bipyridine backbone and the thiourea motif are essential to the activity and enantioselectivity through hydrogen bonding interactions.
Synthesis, characterization and optoelectrochemical properties of poly(1,6-bis(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)hexane) and its copolymer with EDOT
Ak, Metin; Sahmetlioglu, Ertugrul; Toppare, Levent Kamil (Elsevier BV, 2008-09-01)
A new polythiophene derivative was synthesized by electrochemical oxidative polymerization of 1,6-bis(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)hexane (TPH). The structure of the monomer was elucidated by H-1, C-13, MR and mass analyses. The polymer P(TPH) and its copolymer with 3,4-ethylenedioxythiophene (P(TPH-co-EDOT)) were synthesized via potentiostatic electrochemical polymerization. Characterizations of the resulting polymers were performed by cyclic voltammetry (CV), FTIR, UV-vis spectroscopies; and condu...
Synthesis of ferrocenyl pyrazoles by the reaction of (2-formyl-1-chlorovinyl)ferrocene with hydrazines
Zora, Metin (Elsevier BV, 2007-10-15)
Synthesis of ferrocenyl-substituted pyrazoles via the reaction between (2-formyl-1-chlorovinyl)ferrocene and hydrazine derivatives is described. Depending upon the substitution pattern of hydrazine, the reaction affords 1-alkyl/aryl-5-ferrocenylpyrazoles and/or 1-alkyl/ aryl-3-ferrocenylpyrazoles. The reaction appears to be general for a variety of hydrazine derivatives.
Citation Formats
F. Aslanoğlu, “Synthesis of cycloheptadiene annelated dihydrofurane derivatives and design of pyrrolo-pyrrolo-pyrazines and α-alkylidyn-γ-butyrolactones via alkyne cyclization /,” Ph.D. - Doctoral Program, Middle East Technical University, 2018.