Regioselectivity observed in manganese(III) acetate mediated addition of acetylacetone to various alkenes: mechanistic and theoretical studies

Date

2016-10-27

Author

Ceyhan, Selin
Cetinkaya, Yasin
Akdağ, Akın
BALCI, METİN

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

212
views

0
downloads

Various alkenes substituted at the 1,2-positions by 2-thiophenyl, 3-thiophenyl, and phenyl substituted by electron-withdrawing and electron-donating groups were treated with acetylacetone in the presence of Mn(OAc)(3) in acetic acid. In cases where the thiophene ring was connected at the C-2 carbon atom to the double bond, a single regioisomer was formed whereas in case of substitution at the C-3 positions two regioisomers were formed. Stilbene derivatives also gave two regioisomers under the same reaction conditions. However, 1-methoxy-4-(4-nitrostyryl)benzene provided a single cycloaddition product. The observed regioselectivity was discussed in terms of atomic charge distribution on the olefinic double bond carbon atoms. Furthermore, activation barriers for transition states were calculated.

Subject Keywords

Cycloaddition, Substituent effects, Oxidation, Regioselectivity, Mn(OAc)(3)

URI

https://hdl.handle.net/11511/34324

Journal

TETRAHEDRON

DOI

https://doi.org/10.1016/j.tet.2016.09.015

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Electrochemical and chemical oxidation of K(C2H5OCS2),[Ni(C2H5OCS2)(2)] and [N(C2H5)(4)][Ni(C2H5OCS2)(3)] Dag, O; Önal, Ahmet Muhtar; Isci, H (1996-06-26) Electrochemical and chemical oxidation of (Et-Xan(-)), [Ni(Et-Xan)(2)] and [Ni(Et-Xan)(3)](-) (Et-Xan(-) = C2H5OCS2- have been studied by Cyclic Voltammetry and in situ UV-Vis spectroscopy in acetonitrile at room temperature. Cyclic Voltammograms (CV) of Et-Xan(-) and Ni(Et-Xan)(2) display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to Ag/Ag+(0.10 M) electrode. However, CV of Ni(Et-Xan)(3)(-) displays one reversible (-0.15 V) and two irreversible (0.35, 0.80...
Regioselectivity in the Ene reaction of singlet oxygen with cyclic alkenes and application of Ene reaction to stereoselective synthesis of carbaheptopyranose derivatives Doğan, Şengül Dilem; Balcı, Metin; Department of Chemistry (2010) In the first part of this thesis is related to the regioselectivity in ene reaction of singlet oxygen with cyclic alkenes. The photooxygenation of 1-methyl-, 2,3-dimethyl-, 1,4-dimethylcyclohexa-1,4-dienes, 1,2,3,4,5,8-hexahydronaphthalene (16) and 2,3,4,7-tetrahydro-1H-indene (17) which are readily available through Birch reduction, yielded the ene products. The formed endocyclic dienes were trapped by the addition of singlet oxygen to give corresponding bicyclic endoperoxy-hydroperoxides. In the case of 1...
Electrochemical behaviour and electrochemical polymerization of fluoro-substituted anilines Cihaner, A; Önal, Ahmet Muhtar (2002-08-01) The electrochemical behaviour of three fluoro-substituted aniline monomers, 2-fluoroaniline (2FAN), 3-fluoroaniline (3FAN) and 4-fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile-water mixture (1: 1 by volume) using NaClO4 as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin reso...
Genetic polymorphisms of alcohol inducible CYP2E1 in Turkish population Ulusoy, Gülen; Adalı, Orhan; Department of Biochemistry (2004) Cytochrome P4502E1 (CYP2E1), the ethanol-inducible isoform of cytochrome P450 superfamily, catalyzes many low molecular weight endogenous and exogenous compounds, including ethanol, acetone, drugs like acetaminophen and chlorzoxazone, and industrial solvents like benzene and styrene, most of which are carcinogenic. Besides, it has a high capacity to produce reactive oxygen species. CYP2E1 is induced by ethanol and isoniazid, as well by some pathophysiological conditions like diabetes and starvation. CYP2E1 ...
Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(II) and tetraethylammonium tris(ethylxanthato)nickelate(II) Dag, O; Yaman, SO; Önal, Ahmet Muhtar; Isci, H (2001-10-07) Electrochemical and chemical oxidation of S2COEt-, Ni(S2COEt)(2), and [Ni(S2COEt)(3)](-) have been studied by CV and in situ UV-VIS spectroscopy in acetonitrile. Cyclic voltammograms of S2COEt- and Ni(S2COEt)(2) display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to an Ag/Ag+ (0.10 M) electrode. However, the cyclic voltammogram of [Ni(S2COEt)(3)](-) displays one reversible (- 0.15 V) and two irreversible (0.35, 0.80 V) oxidation peaks, referenced to an Ag/Ag...

Citation Formats

S. Ceyhan, Y. Cetinkaya, A. Akdağ, and M. BALCI, “Regioselectivity observed in manganese(III) acetate mediated addition of acetylacetone to various alkenes: mechanistic and theoretical studies,” TETRAHEDRON, pp. 6815–6824, 2016, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/34324.