Nagasawa K, Seto N, Hara C, Ito K
Hokkaido College of Pharmacy, Otaru, Japan.
Yakugaku Zasshi. 1997 Nov;117(10-11):786-99. doi: 10.1248/yakushi1947.117.10-11_786.
The Mitsunobu reaction of commercial 4-hydroxycoumarin with both (R)-(-)- and (S)-(+)-tert-butyl mandelates derived from commercial enantiopure mandelic acids furnished (S)-(+)- and (R)-(-)-tert-butyl O-coumarinylmandelates which were, then, treated with trifluoroacetic acid to give novel crystalline optically pure (S)-(+)- and (R)-(-)-O-coumarinylmandelic acids [SCMOH and RCMOH], respectively in good overall yields. Diastereotopic nonequivalence 1H-NMR examination of the resultant esters and amides without any racemization or kinetic resolution by way of a Steglich's procedure (a DCC-DMAP method) has proved each acid to be a useful, efficient and reliable chiral derivatizing agent for the enantiomeric excess determination of chiral alcohols and amines.
市售的4-羟基香豆素与由市售对映体纯扁桃酸衍生的（R）-（-）-和（S）-（+）-扁桃酸叔丁酯发生 Mitsunobu 反应，生成（S）-（+）-和（R）-（-）-O-香豆素基扁桃酸叔丁酯，然后用三氟乙酸处理，分别以良好的总收率得到新型结晶光学纯的（S）-（+）-和（R）-（-）-O-香豆素基扁桃酸[SCMOH 和 RCMOH]。通过 Steglich 方法（DCC-DMAP 法）对所得酯和酰胺进行非对映异位非等价1H-NMR 检查，未发现任何外消旋或动力学拆分，已证明每种酸都是用于对映体过量测定手性醇和胺的有用、高效且可靠的手性衍生试剂。
