Diastereoisomerism of thiol complexes of arsenic acids and pseudoasymmetry of arsenic: a1H and13C NMR study
作者:John S. Edmonds、Takashi Nakayama、Takuya Kondo、Masatoshi Morita
DOI:10.1002/mrc.1739
日期:2006.2
Diastereoisomeric complexes of methylphenylarsinic acid and (L)‐glutathione could be partially separated by HPLC, but the separated compounds rapidly racemized, presumably by pyramidal inversion at the arsenic atom. Hydrolysis of the diastereoisomeric complexes yielded methylphenylarsinous acid as a pair of enantiomers revealed by a 1H NMR study with an asymmetric lanthanide shift reagent. Methylphenylarsinous
甲基苯胂酸和 (L)-谷胱甘肽的非对映异构复合物可以通过 HPLC 部分分离,但分离的化合物迅速外消旋,推测是由于砷原子的锥体反转。非对映异构复合物的水解产生甲基苯基亚砷酸作为一对对映异构体,通过 1H NMR 研究显示,使用不对称镧系元素位移试剂。甲基苯胂酸也被合成为对映体对,如不对称位移试剂实验所示,通过碘甲基苯胂的水解。1H 和 13C NMR 光谱用于证明苯胂酸与 (R,S)-3-mercapto-1,2-丙二醇和 (R,S)-1-mercapto-2-丙醇的络合,在每种情况下,一对对映体,PhAs[(R)-配体)]2,PhAs[(S)-配体)]2,其中同态配体是非对映异构体,以及一对非对映异构体PhAs[(R)-配体][(S)-配体],它们在假不对称砷原子的构型上彼此不同。版权所有 © 2005 John Wiley & Sons, Ltd.