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Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform

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2012
Authors
Vitnik, Vesna
Vitnik, Željko
Juranić, Ivan
Article (Published version)
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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 carbanion
Source:
Journal of Molecular Modeling, 2012, 18, 10, 4721-4728
Publisher:
  • Springer, New York
Projects:
  • Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-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
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URI
http://cer.ihtm.bg.ac.rs/handle/123456789/1135
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  • Radovi istraživača / Researchers' publications
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IHTM

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