Self-association promoted conformational transition of (3R,4S,8R,9R)-9-[(3, 5-bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine

P. Király, T. Soós, Szilárd Varga, Benedek Vakulya, G. Tárkányi

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The conformational diversity of the (3R,4S,8R,9R)-9-[(3,5- bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine organocatalyst is discussed. Low-temperature NMR experiments confirmed a self-association process, which promotes the quinoline rotation between two intramolecularly hydrogen-bonded monomeric conformers of the catalyst. The balanced population of the coexisting monomeric and dimeric species allowed us to conduct a structural study of a rather complex conformational dynamics of the pure catalyst. The study is extended by a comparison with other members of the bifunctional amine-thiourea organocatalyst family. Changes in themolecular structure of the catalysts influence the interplaybetween intraand intermolecular hydrogen bonding, and yield different extent of catalyst self-association. By assessing the conformation of the individual states, we established the thermodynamic model of a self-association promoted conformational transition.

Original languageEnglish
Pages (from-to)13-19
Number of pages7
JournalMagnetic Resonance in Chemistry
Volume48
Issue number1
DOIs
Publication statusPublished - Jan 2010

Fingerprint

Thioureas
Association reactions
Catalysts
Thiourea
Amines
Conformations
Hydrogen
Hydrogen bonds
Nuclear magnetic resonance
Thermodynamics
(3R,4S,8R,9R)-9-((3,5-bis(trifluoromethyl)phenyl)-thiourea)(9-deoxy)-epi-cinchonine
Experiments
Temperature

Keywords

  • 2D EXSY
  • CH/pi
  • Conformational analysis
  • Dimer
  • Hydrogen bonding
  • NMR
  • Organocatalysis; chemical exchange
  • Quinoline
  • Self-association

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)

Cite this

@article{f15cc74d1bfe450692fb6aa492a443e4,
title = "Self-association promoted conformational transition of (3R,4S,8R,9R)-9-[(3, 5-bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine",
abstract = "The conformational diversity of the (3R,4S,8R,9R)-9-[(3,5- bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine organocatalyst is discussed. Low-temperature NMR experiments confirmed a self-association process, which promotes the quinoline rotation between two intramolecularly hydrogen-bonded monomeric conformers of the catalyst. The balanced population of the coexisting monomeric and dimeric species allowed us to conduct a structural study of a rather complex conformational dynamics of the pure catalyst. The study is extended by a comparison with other members of the bifunctional amine-thiourea organocatalyst family. Changes in themolecular structure of the catalysts influence the interplaybetween intraand intermolecular hydrogen bonding, and yield different extent of catalyst self-association. By assessing the conformation of the individual states, we established the thermodynamic model of a self-association promoted conformational transition.",
keywords = "2D EXSY, CH/pi, Conformational analysis, Dimer, Hydrogen bonding, NMR, Organocatalysis; chemical exchange, Quinoline, Self-association",
author = "P. Kir{\'a}ly and T. So{\'o}s and Szil{\'a}rd Varga and Benedek Vakulya and G. T{\'a}rk{\'a}nyi",
year = "2010",
month = "1",
doi = "10.1002/mrc.2531",
language = "English",
volume = "48",
pages = "13--19",
journal = "Magnetic Resonance in Chemistry",
issn = "0749-1581",
publisher = "John Wiley and Sons Ltd",
number = "1",

}

TY - JOUR

T1 - Self-association promoted conformational transition of (3R,4S,8R,9R)-9-[(3, 5-bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine

AU - Király, P.

AU - Soós, T.

AU - Varga, Szilárd

AU - Vakulya, Benedek

AU - Tárkányi, G.

PY - 2010/1

Y1 - 2010/1

N2 - The conformational diversity of the (3R,4S,8R,9R)-9-[(3,5- bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine organocatalyst is discussed. Low-temperature NMR experiments confirmed a self-association process, which promotes the quinoline rotation between two intramolecularly hydrogen-bonded monomeric conformers of the catalyst. The balanced population of the coexisting monomeric and dimeric species allowed us to conduct a structural study of a rather complex conformational dynamics of the pure catalyst. The study is extended by a comparison with other members of the bifunctional amine-thiourea organocatalyst family. Changes in themolecular structure of the catalysts influence the interplaybetween intraand intermolecular hydrogen bonding, and yield different extent of catalyst self-association. By assessing the conformation of the individual states, we established the thermodynamic model of a self-association promoted conformational transition.

AB - The conformational diversity of the (3R,4S,8R,9R)-9-[(3,5- bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine organocatalyst is discussed. Low-temperature NMR experiments confirmed a self-association process, which promotes the quinoline rotation between two intramolecularly hydrogen-bonded monomeric conformers of the catalyst. The balanced population of the coexisting monomeric and dimeric species allowed us to conduct a structural study of a rather complex conformational dynamics of the pure catalyst. The study is extended by a comparison with other members of the bifunctional amine-thiourea organocatalyst family. Changes in themolecular structure of the catalysts influence the interplaybetween intraand intermolecular hydrogen bonding, and yield different extent of catalyst self-association. By assessing the conformation of the individual states, we established the thermodynamic model of a self-association promoted conformational transition.

KW - 2D EXSY

KW - CH/pi

KW - Conformational analysis

KW - Dimer

KW - Hydrogen bonding

KW - NMR

KW - Organocatalysis; chemical exchange

KW - Quinoline

KW - Self-association

UR - http://www.scopus.com/inward/record.url?scp=73949129298&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=73949129298&partnerID=8YFLogxK

U2 - 10.1002/mrc.2531

DO - 10.1002/mrc.2531

M3 - Article

VL - 48

SP - 13

EP - 19

JO - Magnetic Resonance in Chemistry

JF - Magnetic Resonance in Chemistry

SN - 0749-1581

IS - 1

ER -