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On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane

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2012
Authors
Drakulić, Branko
Marinković, Aleksandar D.
Juranić, Ivan
Article (Published version)
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Abstract
Rate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane in ethanol at 30 C were determined, and correlated with substituent constants using classical Hammett and related methods. Statistically valid results for the para-substituted compounds were obtained by the Swain–Lupton approach. The compounds studied had significant conformational mobility due to seven rotatable bonds in their backbone. Going beyond the classical Hammett approach, we established a relatively fast procedure to find the optimal conformations that can be used in linear free-energy relationships, combining molecular dynamics with semiempirical calculations, and calculations using a higher level of theory (DFT and MP2). Fair correlations were observed with frontier orbitals, allowing inclusion of ortho-substituted derivatives and clarifying artifact-like data, as perceived by the Hammett-type approach.
Keywords:
Conformational space / Rate constants / Linear free-energy relationships / Frontier orbitals
Source:
Tetrahedron Letters, 2012, 53, 5, 553-556
Publisher:
  • Amsterdam : Elsevier
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 (EU-261499)

DOI: 10.1016/j.tetlet.2011.11.097

ISSN: 00404039

WoS: 000300029000021

Scopus: 2-s2.0-84962433241
[ Google Scholar ]
URI
http://cer.ihtm.bg.ac.rs/handle/123456789/3438
Collections
  • Radovi istraživača / Researchers' publications
Institution
IHTM
TY  - JOUR
AU  - Drakulić, Branko
AU  - Marinković, Aleksandar D.
AU  - Juranić, Ivan
PY  - 2012
UR  - http://cer.ihtm.bg.ac.rs/handle/123456789/3438
AB  - Rate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids
with diphenyldiazomethane in ethanol at 30  C were determined, and correlated with substituent constants
using classical Hammett and related methods. Statistically valid results for the para-substituted
compounds were obtained by the Swain–Lupton approach. The compounds studied had significant conformational
mobility due to seven rotatable bonds in their backbone. Going beyond the classical Hammett
approach, we established a relatively fast procedure to find the optimal conformations that can
be used in linear free-energy relationships, combining molecular dynamics with semiempirical calculations,
and calculations using a higher level of theory (DFT and MP2). Fair correlations were observed with
frontier orbitals, allowing inclusion of ortho-substituted derivatives and clarifying artifact-like data, as
perceived by the Hammett-type approach.
PB  - Amsterdam : Elsevier
T2  - Tetrahedron Letters
T1  - On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane
VL  - 53
IS  - 5
SP  - 553
EP  - 556
DO  - 10.1016/j.tetlet.2011.11.097
ER  - 
@article{
author = "Drakulić, Branko and Marinković, Aleksandar D. and Juranić, Ivan",
year = "2012",
url = "http://cer.ihtm.bg.ac.rs/handle/123456789/3438",
abstract = "Rate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids
with diphenyldiazomethane in ethanol at 30  C were determined, and correlated with substituent constants
using classical Hammett and related methods. Statistically valid results for the para-substituted
compounds were obtained by the Swain–Lupton approach. The compounds studied had significant conformational
mobility due to seven rotatable bonds in their backbone. Going beyond the classical Hammett
approach, we established a relatively fast procedure to find the optimal conformations that can
be used in linear free-energy relationships, combining molecular dynamics with semiempirical calculations,
and calculations using a higher level of theory (DFT and MP2). Fair correlations were observed with
frontier orbitals, allowing inclusion of ortho-substituted derivatives and clarifying artifact-like data, as
perceived by the Hammett-type approach.",
publisher = "Amsterdam : Elsevier",
journal = "Tetrahedron Letters",
title = "On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane",
volume = "53",
number = "5",
pages = "553-556",
doi = "10.1016/j.tetlet.2011.11.097"
}
Drakulić B, Marinković AD, Juranić I. On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane. Tetrahedron Letters. 2012;53(5):553-556
Drakulić, B., Marinković, A. D.,& Juranić, I. (2012). On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane.
Tetrahedron LettersAmsterdam : Elsevier., 53(5), 553-556.
https://doi.org/10.1016/j.tetlet.2011.11.097
Drakulić Branko, Marinković Aleksandar D., Juranić Ivan, "On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane" 53, no. 5 (2012):553-556,
https://doi.org/10.1016/j.tetlet.2011.11.097 .

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