Synthesis, Structure, and Thermolysis of a Pentacoordinate 1,2-Oxastibetane

Isomeric pentacoordinate 1,2-oxastibetanes bearing the Martin ligand have been synthesized by the reactions of bromo(2-hydroxyalkyl)stiboranes with sodium hydride of which one of the isomers was characterized by X-ray crystallographic analysis and NMR spectroscopy. Thermolysis of the isomer shown (CD3CN, 140 °C) afforded the oxirane with retention of configuration, while its thermolyses in the presence of lithium bromide and LiBPh4·3DME provided the oxirane with inversion of configuration and the olefin. The addition of the salts in the thermolyses of this pentacoordinate 1,2-oxastibetane controls both the stereochemistry of the oxirane formed and the ratios of the three main products.

具有 Martin 配体的异构五配位 1,2-氧代噻并噻烷通过溴代(2-羟基烷基)锑烷与钠氢化物反应合成。其中一种异构体经 X 射线晶体学分析和核磁共振波谱学表征。所示异构体（CD3CN，140 °C）的热解反应保留了构型，而其在溴化锂和 LiBPh4·3DME 存在下的热解则提供了构型和烯烃的构型反转。在此五配位 1,2-氧代噻并噻烷的热解过程中，盐的加入控制了生成的环氧烷的立体化学以及三种主要产物的比例。