TAUTOMERISM AND STEREOCHEMISTRY OF HYPERICIN - FORCE-FIELD, NMR, AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS

被引：65

作者：

ETZLSTORFER, C ^{[1
]}

FALK, H ^{[1
]}

MULLER, N ^{[1
]}

SCHMITZBERGER, W ^{[1
]}

WAGNER, UG ^{[1
]}

机构：

[1] GRAZ UNIV,INST PHYS CHEM,A-8010 GRAZ,AUSTRIA

来源：

MONATSHEFTE FUR CHEMIE | 1993年 / 124卷 / 6-7期

关键词：

HYPERICIN; PSEUDOHYPERICIN; FORCE FIELD CALCULATIONS; X-RAY CRYSTALLOGRAPHY; TAUTOMERISM; INTERCONVERSION BARRIER;

D O I：

10.1007/BF00817311

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stereochemistry and tautomerism of hypericin, pseudohypericin, and several of their partial structure models were investigated using an MM2 derived force field method. Besides the ''propeller'' type conformer, which was also found by the X-ray crystallographic study, the complicated energy hypersurface was shown to contain a novel ''double-butterfly'' conformer of similar stability. The upper limit interconversion barrier between these conformers and their enantiomers was found to be in the order of 115 kJ/mol. H-1-NMR experiments suggested a lower limit interconversion barrier of at least 80 kJ/mol. From the ten tautomers possible in principle, the 7,14-species was derived to be the most stable one by at least 48 kJ/mol.

引用

页码：751 / 761

页数：11

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