Two convenient methods for the synthesis of chiral 2-ethynylaziridines from
natural alpha-amino acids are described. Sodium hydride-promoted aziridina
tion of mesylates of 4-arylsulfonylamino-2-bromoalk-2-en-1-ols yields trans
- 2-(1-bromovinyl)aziridines in a highly stereoselective manner, and subseq
uent dehydrobromination of the aziridines by potassium tert-butoxide gives
separable stereoisomeric mixtures of trans- and cis-2-ethynylaziridines in
enantiomerically pure forms (> 98% ee). Simple synthesis of 2-ethynylazirid
ines with high optical purities (91-98% ee) from chiral amino alcohols bear
ing an ethynyl group under Mitsunobu conditions is also presented.