New approaches to polysubstituted pyrroles and pyrrolinones from alpha-cyanomethyl-beta-ketoesters

Demir, Ayhan Sıtkı
Emrullahoglu, Mustafa
Ardahan, Gulben
In this present paper, we report the efficient, regioselective one-pot synthesis of 5-alkoxy and 5-alkylsulfanylpyrrole-3-carboxylates in high yields via the zinc perchlorate-catalyzed addition of alcohols and thiols to the nitrile carbon of alpha-cyanornethyl-beta-ketoesters followed by annulation. The addition-annulation process is undertaken in aqueous solution to give 4,5-dihydro-5-oxo-1H-pyrrole-beta-carboxylates (pyrrolinones) in good yields. These 4,5-dihydro-5-oxo-1H-pyrrole-3-carboxylates are also obtained by the hydrolysis of 5-alkoxypyrrole-3-carboxylates.


A novel one-pot, three-component reaction for the synthesis of isocoumarin-condensed pyrazoles
OZCAN, Sevil; Dengiz, Çağatay; DELIOMEROGLU, Murat K.; ŞAHİN, Ertan; BALCI, METİN (Elsevier BV, 2011-03-30)
The one-pot, three-component reaction of substituted homophthalic anhydrides with hydrazine in DMF as solvent and reactant, at reflux temperature, afforded isochromeno[3,4-c]pyrazole-5(2H)-one derivatives in high yields. The mechanism and roles of the substrates were investigated and it was found that cyclic hydrazides were formed as intermediates.
Synthesis of thio- and furan-fused heterocycles: furopyranone, furopyrrolone, and thienopyrrolone derivatives
ERGUN, Merve; Dengiz, Çağatay; OZER, Merve Sinem; ŞAHİN, Ertan; BALCI, METİN (Elsevier BV, 2014-09-02)
We report herein the synthesis of a novel class of compounds, ethyl 4-oxo-4H-furo[3,2-c]pyran-6-yl carbonate, (7E)-7-[(dimethylamino)methylene]-4H-furo[3,2-c]pyran-4,6(7H)-dione, 5-oxo-N-phenyl-2,5-dihydro-4H-furo[3,2-b]pyrrole-4-carboxamide,and 5-oxo-N-phenyl-5,6-dihydro-4H-thieno[3,2-b] pyrrole-4-carboxamide starting from the corresponding acid derivatives. Intramolecular cyclization in the presence of thionyl chloride formed the target fused ring systems. Additional transformation was seen in the cycliza...
A novel synthesis of 1,2,4-oxadiazoles and isoxazoles
KIVRAK, Arif; Zora, Metin (Elsevier BV, 2014-01-28)
A novel synthesis of 1,2,4-oxadiazoles and isoxazoles is described by utilizing the reactions between amidoximes and alpha,beta-alkynic aldehydes and/or ketones. Conjugate addition products, obtained from amidoximes and alpha,beta-alkynic aldehydes and/or ketones, afford 1,2,4-oxadiazoles and isoxazoles when treated with bases and acids, respectively. 1,2,4-Oxadiazoles can also be synthesized directly from amidoximes and alpha,beta-alkynic aldehydes in a one-pot manner under basic conditions. The reactions ...
An effective new synthesis of 2-aminopyrrole-4-carboxylates
Demir, Ayhan Sıtkı; Emrullahoglu, M (Elsevier BV, 2005-10-31)
Efficient syntheses of 2-aminopyrroles are presented starting from beta-dicarbonyl compounds, bromoacetonitrile, and amines. Alkylation of beta-dicarbonyl compounds with bromoacetonitrile furnished alpha-cyanomethyl-beta-dicarbonyl compounds. The condensation reaction of alpha-cyanomethyl-beta-dicarbonyl compounds with amines catalyzed by p-TsOH affords the corresponding enamines in good yields. Base catalyzed cyclization via the addition of an amine moiety to the carbon-nitrogen triple bond of nitrile furn...
Synthesis of chiral acetoxy lactones via the Baeyer-Villiger oxidation of cyclic aromatic acetoxy ketones
Demir, Ayhan Sıtkı; Aybey, Asuman (Elsevier BV, 2008-12-01)
The alpha-acetoxylation of indanones and tetralones by using Mn(OAc)(3) followed by the enzyme catalyzed kinetic resolution of acetoxy ketones furnished both of the enantiomers of alpha-acetoxy ketones in good chemical and optical yields. The Baeyer-Villiger oxidation of alpha-acetoxy ketones with m-CPBA, CF(3)SO(3)H, and CH(2)O(2), at rt gives the corresponding lactones without racemization. The acetoxy ketone moiety migrates selectively in order to form lactones. The mild hydrolysis of lactones affords ph...
Citation Formats
A. S. Demir, M. Emrullahoglu, and G. Ardahan, “New approaches to polysubstituted pyrroles and pyrrolinones from alpha-cyanomethyl-beta-ketoesters,” TETRAHEDRON, pp. 461–468, 2007, Accessed: 00, 2020. [Online]. Available: