Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform
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2012
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Metapodaci
Prikaz svih podataka o dokumentuApstrakt
The extensive computation study was done to elucidate the mechanism of formation dibromoepoxide from cyclohexanone and bromoform. In this reaction, the formation of dihaloepoxide 2 is postulated as a key step that determines the distribution and stereochemistry of products. Two mechanistic paths of reaction were investigated: the addition of dibromocarbene to carbonyl group of ketone, and the addition of tribromomethyl carbanion to the same (C=O) group. The mechanisms for the addition reactions of dibromocarbenes and tribromomethyl carbanions with cyclohexanone have been investigated using ab initio HF/6-311++G** and MP2/6-311+G* level of theory. Solvent effects on these reactions have been explored by calculations which included a continuum polarizable conductor model (CPCM) for the solvent (H2O). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies.
Ključne reči:
Ab initio calculations / Dibromocarbene / Dihaloepoxides / Reaction mechanisms / Tribromomethyl carbanionIzvor:
Journal of Molecular Modeling, 2012, 18, 10, 4721-4728Izdavač:
- Springer, New York
Finansiranje / projekti:
- Racionalni dizajn i sinteza biološki aktivnih i koordinacionih jedinjenja i funkcionalnih materijala, relevantnih u (bio)nanotehnologiji (RS-MESTD-Basic Research (BR or ON)-172035)
- High-Performance Computing Infrastructure for South East Europe's Research Communities European proj
DOI: 10.1007/s00894-012-1468-2
ISSN: 1610-2940
PubMed: 22660943
WoS: 000309862000015
Scopus: 2-s2.0-84870560097
Institucija/grupa
IHTMTY - JOUR AU - Vitnik, Vesna AU - Vitnik, Željko AU - Juranić, Ivan PY - 2012 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1135 AB - The extensive computation study was done to elucidate the mechanism of formation dibromoepoxide from cyclohexanone and bromoform. In this reaction, the formation of dihaloepoxide 2 is postulated as a key step that determines the distribution and stereochemistry of products. Two mechanistic paths of reaction were investigated: the addition of dibromocarbene to carbonyl group of ketone, and the addition of tribromomethyl carbanion to the same (C=O) group. The mechanisms for the addition reactions of dibromocarbenes and tribromomethyl carbanions with cyclohexanone have been investigated using ab initio HF/6-311++G** and MP2/6-311+G* level of theory. Solvent effects on these reactions have been explored by calculations which included a continuum polarizable conductor model (CPCM) for the solvent (H2O). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies. PB - Springer, New York T2 - Journal of Molecular Modeling T1 - Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform VL - 18 IS - 10 SP - 4721 EP - 4728 DO - 10.1007/s00894-012-1468-2 ER -
@article{ author = "Vitnik, Vesna and Vitnik, Željko and Juranić, Ivan", year = "2012", abstract = "The extensive computation study was done to elucidate the mechanism of formation dibromoepoxide from cyclohexanone and bromoform. In this reaction, the formation of dihaloepoxide 2 is postulated as a key step that determines the distribution and stereochemistry of products. Two mechanistic paths of reaction were investigated: the addition of dibromocarbene to carbonyl group of ketone, and the addition of tribromomethyl carbanion to the same (C=O) group. The mechanisms for the addition reactions of dibromocarbenes and tribromomethyl carbanions with cyclohexanone have been investigated using ab initio HF/6-311++G** and MP2/6-311+G* level of theory. Solvent effects on these reactions have been explored by calculations which included a continuum polarizable conductor model (CPCM) for the solvent (H2O). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies.", publisher = "Springer, New York", journal = "Journal of Molecular Modeling", title = "Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform", volume = "18", number = "10", pages = "4721-4728", doi = "10.1007/s00894-012-1468-2" }
Vitnik, V., Vitnik, Ž.,& Juranić, I.. (2012). Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform. in Journal of Molecular Modeling Springer, New York., 18(10), 4721-4728. https://doi.org/10.1007/s00894-012-1468-2
Vitnik V, Vitnik Ž, Juranić I. Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform. in Journal of Molecular Modeling. 2012;18(10):4721-4728. doi:10.1007/s00894-012-1468-2 .
Vitnik, Vesna, Vitnik, Željko, Juranić, Ivan, "Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform" in Journal of Molecular Modeling, 18, no. 10 (2012):4721-4728, https://doi.org/10.1007/s00894-012-1468-2 . .