Systematic conformational search analysis of the SRR and RRR epimers of 7-hydroxymatairesinol

Dario Duca, Giampaolo Barone, Dmitry Yu. Murzin

Risultato della ricerca: Article

4 Citazioni (Scopus)

Abstract

An extensive and systematic conformational search was performed on the two epimers of the natural lignan 7-hydroxymatairesinol (HMR), by means of a home-made Systematic Conformational Search Analysis (SCSA) code, designed to select more and more stable conformers through sequential geometry optimization of trial structures at increasing levels of calculation theory. In the present case, the starting molecular structures were selected by the semi-empirical AM1 method and filtered – i.e. decreased in number by choosing the more stable species – on the basis of their energy calculated by the HF method and the 6-31G(d) basis set. The geometries obtained were further refined by performing density functional theory (DFT) optimizations, using the B3LYP functional and the 6 31G(d,p) basis set, both in vacuo and in ethanol solution. This procedure allowed us to isolate, at a high level of theory, three groups of epimer conformers characterized by open, semi-folded, and folded conformations. Moreover, the SCSA allowed us to describe a conformational space made-up by about 20 species for each of the two epimers. The corresponding energy content of these species was within 27 kJ molS1 from the absolute minimum found, both in vacuo and in ethanol solution. The conformational analysis, followed by the inspection of the stereochemistry of the two most stable conformers of both epimers, provides support in rationalizing the proposed reaction mechanism of the catalytic hydrogenolysis of the HMR to matairesinol (MAT).
Lingua originaleEnglish
pagine (da-a)141-147
Numero di pagine7
RivistaJournal of Physical Organic Chemistry
Volume23
Stato di pubblicazionePublished - 2010

Fingerprint

ethyl alcohol
Ethanol
hydrogenolysis
Lignans
Hydrogenolysis
Stereochemistry
optimization
Geometry
stereochemistry
geometry
Molecular structure
Density functional theory
Conformations
inspection
molecular structure
Inspection
density functional theory
energy
hydroxymatairesinol
matairesinol

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cita questo

@article{d1617f212f59493788b0c203447770f2,
title = "Systematic conformational search analysis of the SRR and RRR epimers of 7-hydroxymatairesinol",
abstract = "An extensive and systematic conformational search was performed on the two epimers of the natural lignan 7-hydroxymatairesinol (HMR), by means of a home-made Systematic Conformational Search Analysis (SCSA) code, designed to select more and more stable conformers through sequential geometry optimization of trial structures at increasing levels of calculation theory. In the present case, the starting molecular structures were selected by the semi-empirical AM1 method and filtered – i.e. decreased in number by choosing the more stable species – on the basis of their energy calculated by the HF method and the 6-31G(d) basis set. The geometries obtained were further refined by performing density functional theory (DFT) optimizations, using the B3LYP functional and the 6 31G(d,p) basis set, both in vacuo and in ethanol solution. This procedure allowed us to isolate, at a high level of theory, three groups of epimer conformers characterized by open, semi-folded, and folded conformations. Moreover, the SCSA allowed us to describe a conformational space made-up by about 20 species for each of the two epimers. The corresponding energy content of these species was within 27 kJ molS1 from the absolute minimum found, both in vacuo and in ethanol solution. The conformational analysis, followed by the inspection of the stereochemistry of the two most stable conformers of both epimers, provides support in rationalizing the proposed reaction mechanism of the catalytic hydrogenolysis of the HMR to matairesinol (MAT).",
keywords = "7-hydroxymatairesinol quantum chemical study, DFT calculations, structure–reactivity relationship, systematic conformational search analysis",
author = "Dario Duca and Giampaolo Barone and {Yu. Murzin}, Dmitry",
year = "2010",
language = "English",
volume = "23",
pages = "141--147",
journal = "Journal of Physical Organic Chemistry",
issn = "0894-3230",
publisher = "John Wiley and Sons Ltd",

}

TY - JOUR

T1 - Systematic conformational search analysis of the SRR and RRR epimers of 7-hydroxymatairesinol

AU - Duca, Dario

AU - Barone, Giampaolo

AU - Yu. Murzin, Dmitry

PY - 2010

Y1 - 2010

N2 - An extensive and systematic conformational search was performed on the two epimers of the natural lignan 7-hydroxymatairesinol (HMR), by means of a home-made Systematic Conformational Search Analysis (SCSA) code, designed to select more and more stable conformers through sequential geometry optimization of trial structures at increasing levels of calculation theory. In the present case, the starting molecular structures were selected by the semi-empirical AM1 method and filtered – i.e. decreased in number by choosing the more stable species – on the basis of their energy calculated by the HF method and the 6-31G(d) basis set. The geometries obtained were further refined by performing density functional theory (DFT) optimizations, using the B3LYP functional and the 6 31G(d,p) basis set, both in vacuo and in ethanol solution. This procedure allowed us to isolate, at a high level of theory, three groups of epimer conformers characterized by open, semi-folded, and folded conformations. Moreover, the SCSA allowed us to describe a conformational space made-up by about 20 species for each of the two epimers. The corresponding energy content of these species was within 27 kJ molS1 from the absolute minimum found, both in vacuo and in ethanol solution. The conformational analysis, followed by the inspection of the stereochemistry of the two most stable conformers of both epimers, provides support in rationalizing the proposed reaction mechanism of the catalytic hydrogenolysis of the HMR to matairesinol (MAT).

AB - An extensive and systematic conformational search was performed on the two epimers of the natural lignan 7-hydroxymatairesinol (HMR), by means of a home-made Systematic Conformational Search Analysis (SCSA) code, designed to select more and more stable conformers through sequential geometry optimization of trial structures at increasing levels of calculation theory. In the present case, the starting molecular structures were selected by the semi-empirical AM1 method and filtered – i.e. decreased in number by choosing the more stable species – on the basis of their energy calculated by the HF method and the 6-31G(d) basis set. The geometries obtained were further refined by performing density functional theory (DFT) optimizations, using the B3LYP functional and the 6 31G(d,p) basis set, both in vacuo and in ethanol solution. This procedure allowed us to isolate, at a high level of theory, three groups of epimer conformers characterized by open, semi-folded, and folded conformations. Moreover, the SCSA allowed us to describe a conformational space made-up by about 20 species for each of the two epimers. The corresponding energy content of these species was within 27 kJ molS1 from the absolute minimum found, both in vacuo and in ethanol solution. The conformational analysis, followed by the inspection of the stereochemistry of the two most stable conformers of both epimers, provides support in rationalizing the proposed reaction mechanism of the catalytic hydrogenolysis of the HMR to matairesinol (MAT).

KW - 7-hydroxymatairesinol quantum chemical study

KW - DFT calculations

KW - structure–reactivity relationship

KW - systematic conformational search analysis

UR - http://hdl.handle.net/10447/50213

M3 - Article

VL - 23

SP - 141

EP - 147

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

SN - 0894-3230

ER -