Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform
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.
Keywords:
Ab initio calculations / Dibromocarbene / Dihaloepoxides / Reaction mechanisms / Tribromomethyl carbanionSource:
Journal of Molecular Modeling, 2012, 18, 10, 4721-4728Publisher:
- Springer, New York
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (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
Collections
Institution/Community
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 . .