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
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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.
Ključne reči:
Conformational space / Rate constants / Linear free-energy relationships / Frontier orbitalsIzvor:
Tetrahedron Letters, 2012, 53, 5, 553-556Izdavač:
- Amsterdam : Elsevier
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 (EU-FP7-261499)
DOI: 10.1016/j.tetlet.2011.11.097
ISSN: 00404039
WoS: 000300029000021
Scopus: 2-s2.0-84962433241
Institucija/grupa
IHTMTY - JOUR AU - Drakulić, Branko AU - Marinković, Aleksandar D. AU - Juranić, Ivan PY - 2012 UR - https://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", 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, 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. in Tetrahedron Letters Amsterdam : Elsevier., 53(5), 553-556. https://doi.org/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. in Tetrahedron Letters. 2012;53(5):553-556. doi: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" in Tetrahedron Letters, 53, no. 5 (2012):553-556, https://doi.org/10.1016/j.tetlet.2011.11.097 . .