Guang Jie, Hopson Russell, Williard Paul G
Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
J Org Chem. 2015 Sep 18;80(18):9102-7. doi: 10.1021/acs.joc.5b01457. Epub 2015 Sep 9.
We report extension of the D-FW analysis using referenced (2)H DOSY. This technique was developed in response to limitations due to peak overlay in (1)H DOSY spectra. We find a corresponding linear relationship (R(2) > 0.99) between log D and log FW as the basis of the D-FW analysis. The solution-state structure of THF solvated lithium diisopropyl amide (LDA) in hydrocarbon solvent was chosen to demonstrate the reliability of the methodology. We observe an equilibrium between monosolvated and disolvated dimeric LDA complexes at room temperature. Additionally we demonstrate the application of the (2)H D-FW analysis using a compound with an exchangeable proton that is readily labeled with (2)H. Hence, the (2)H DOSY D-FW analysis is shown to provide results consistent with the (1)H DOSY method, thereby greatly extending the applicability of the D-FW analysis.
我们报告了使用参比氘（²H）扩散有序光谱（DOSY）对扩散系数-流体动力学半径（D-FW）分析的扩展。该技术是针对¹H DOSY光谱中峰重叠的局限性而开发的。我们发现log D与log FW之间存在相应的线性关系（R²>0.99），作为D-FW分析的基础。选择烃类溶剂中四氢呋喃溶剂化的二异丙基氨基锂（LDA）的溶液态结构来证明该方法的可靠性。我们观察到在室温下单溶剂化和双溶剂化二聚体LDA配合物之间的平衡。此外，我们展示了使用具有可被²H轻松标记的可交换质子的化合物进行²H D-FW分析的应用。因此，²H DOSY D-FW分析显示出与¹H DOSY方法一致的结果，从而大大扩展了D-FW分析的适用性。
