Assignment of the absolute configuration of β-chiral primary alcohols by NMR:: Scope and limitations

被引:60
作者
Latypov, SK
Ferreiro, MJ
Quiñoá, E
Riguera, R [1 ]
机构
[1] Univ Santiago de Compostela, Fac Quim, Dept Quim Organ, Santiago De Compostela 15706, Spain
[2] Univ Santiago de Compostela, Inst Acuicultura, Santiago De Compostela 15706, Spain
[3] Russian Acad Sci, Inst Organ & Phys Chem, Kazan, Tatarstan, Russia
关键词
D O I
10.1021/ja972550b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The prediction of the absolute configuration of beta-chiral primary alcohols from the H-1 NMR spectra of their esters with (R)- and (S)-9-anthrylmethoxyacetic acids (9-AMA, 3) is discussed. Low-temperature NMR experiments, MM, semiempirical, ab initio, and aromatic shielding effect calculations allowed the identification of the main conformers and showed that, in all alcohols for which the calculated Delta E-ag (CVff) is in the range of 0.7-1.5 kcal/mol, conformer a/a is the most stable. A simple model for the assignment of the absolute configuration from NMR data is presented and its reliability corroborated with alcohols (8-20) of known configuration. Nevertheless, cyclic alcohols 21-23 have much higher Delta E-ag values (2.2-3.1 kcaV mel) due to their different conformational composition, and their absolute configuration cannot be reliably predicted by this method.
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收藏
页码:4741 / 4751
页数:11
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