Aziridine Formation with Retention of Configuration from a Pentacoordinated 1,2-Thiazetidine Bearing Two Chiral Centers at the 3-and 4-Positions

作者：Daicho Yuya; Watanabe Yuki; Kano Naokazu; Yukimoto Mariko; Minoura Mao; Kawashima Takayuki^*

来源：Bulletin of the Chemical Society of Japan, 2014, 87(9): 1005-1012.

DOI：10.1246/bcsj.20140132

Tetracoordinated and pentacoordinated 1,2-thiazetidines bearing the Martin ligand, trans-5 and trans-6, were synthesized as stable compounds. The X-ray crystallographic analyses showed that trans-5 and trans-6 have distorted pseudotrigonal bipyramidal (pseudo-TBP) and TBP structures, respectively, and that the two phenyl groups at the 3- and 4-positions of both compounds are cis to each other. Thermal isomerization of the aziridine cis-11, which is considered a thermolysis product of trans-6, occurred even at relatively low temperature (100 degrees C) in solution and made it difficult to determine the stereochemistry of the aziridine formation from trans-6 in solution. Flash vacuum pyrolysis, which potentially prevents the isomerization of the product, was applied to trans-6 to give eventually the stereochemistry-retained aziridine cis-11. This result indicates a ligand coupling pathway in the aziridine formation process from trans-6.

• 出版日期2014-9-15