Lesot Philippe, Lafon Olivier, Courtieu Jacques, Berdagué Philippe
Laboratoire de Chimie Structurale Organique, CNRS UMR 8074, ICMMO, Bât. 410, Université de Paris-Sud, 91405 Orsay cedex, France.
Chemistry. 2004 Aug 6;10(15):3741-6. doi: 10.1002/chem.200400065.
We examined and discuss the proton- and deuterium-decoupled carbon-13 1D spectrum of a molecule, chiral by virtue of the isotopic substitution, dissolved in a chiral oriented medium which simultaneously exhibits chiral discrimination, enantiomeric enrichment and isotope effect. Using the 1-deutero-(2',3',4',5',6'-pentadeuterophenyl)phenylmethanol orientationally ordered in a chiral nematic liquid crystal as illustrative example, we point out three important features. First, we demonstrate that the absolute assignment of the pro-R/pro-S character may be derived from the absolute configuration of the isotopically chiral analogue. Second, we report evidence that isotopic effect on (13)C chemical shift anisotropy is negligible in a weakly orienting solvent. Third, we definitely establish that the molecular orientation of prochiral C(s) symmetry molecules and their parent compounds that are chiral by virtue of the isotopic substitution is the same.
我们研究并讨论了一种因同位素取代而具有手性的分子溶解于同时表现出手性识别、对映体富集和同位素效应的手性取向介质中的质子去耦和氘去耦碳-13 一维谱。以在手性向列型液晶中取向有序的1-氘代-(2',3',4',5',6'-五氘代苯基)苯甲醇为例，我们指出三个重要特征。第一，我们证明了前手性R/前手性S特征的绝对归属可从同位素手性类似物的绝对构型推导得出。第二，我们报告了在弱取向溶剂中，同位素对（13）C化学位移各向异性的影响可忽略不计的证据。第三，我们明确确定了前手性C(s)对称分子及其因同位素取代而具有手性的母体化合物的分子取向是相同的。
