Optically active 3-amino-2H-azirines as synthons for enantiomerically pure alpha,alpha-disubstituted alpha-amino acids: Syntheses of isovaline synthons and a segment of Trichotoxin A-50

被引:49
作者
Bucher, CB [1 ]
Heimgartner, H [1 ]
机构
[1] UNIV ZURICH,INST ORGAN CHEM,CH-8057 ZURICH,SWITZERLAND
关键词
D O I
10.1002/hlca.19960790713
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis of a novel 3-amino-2-methyl-2-[2-(phenylsulfonyl)ethyl]-2H-azirine derivative 12 with a chiral substituent at the amino group is described. Chromatographic separation of the diastereoisomer mixture gave pure diastereoisomers which, after an electrochemical cleavage of the phenylsulfonyl group, yielded the (S)- and (R)-isovalin (Iva) synthons 13a and 13b, respectively. The absolute configuration of the precursor molecule 12b was established by X-ray crystallography. The Iva synthons were successfully used in the synthesis of the C-terminal pentapeptide Z-Leu-Aib-(R)-Iva-Gln-Valoi of the peptaibole Trichotoxin A-50 and its epimer.
引用
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页码:1903 / 1915
页数:13
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