Autoassembling of the cage structures - 11. Absolute configuration and chiroptical properties of 1,4-di-tert-butyl-2,5-dioxabicyclo[2.2.1]heptane-3,6-dione enantiomers

被引:3
作者
Vystorop, IV [1 ]
Kostyanovsky, RG
机构
[1] Russian Acad Sci, Inst Chem Phys, Chernogolovka 142432, Moscow Region, Russia
[2] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow 117977, Russia
关键词
2,5-dioxanorbornane derivatives; absolute configuration; enantiomeric dilactones; diastereomeric lactonamides; circular dichroism spectra;
D O I
10.1007/BF02495516
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Enantiomeric dilactones ((1R,4R)-(+)-1 and (1S,4S)-(-)-1) of alpha,alpha'-dihydroxy-alpha,alpha'-di-tert-butylglutaric acid have been prepared. The Cotton effect sign of the n-->pi*-transition of the lactone chromophore in enantiomers I is determined by the contribution of the uncompensated bonds of the delta-dilactone ring, but not by that of the gamma-monolactone ring of 1. The correlation of the Cotton effect sign of the n-->pi*-transition with the chirality of the cage structure and the absolute configuration for the series of 1,4-dialkyldilactones of type 1 has been suggested. The contribution of the pseudo-a-oriented amide group to the Cotton effect sign of the lactone n-->pi*-transition (the effect of the third chiral sphere) in diastereomeric lactonamides 2a,b predominates over that of the nonplanar bonds of the heterocycle (over the effect of the second chiral sphere).
引用
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页码:107 / 114
页数:8
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