School of Chemistry, University of East Anglia, Norwich Research Park, NR4 7TJ, UK.
Org Lett. 2013 Aug 2;15(15):3805-7. doi: 10.1021/ol400804b. Epub 2013 Jul 22.
A much improved synthetic route to malonic acid half thioesters (MAHTs) and oxyesters (MAHOs), the easy incorporation of deuterium labeling expecially in MAHTs, and an unexpectedly large difference in enolization chemistry between MAHTs and MAHOs are reported. Density functional theory calculations explore the origins of this difference and identify an additional MAHT molecular orbital which increases delocalization between sulfur and the enol in both cisoid and transoid forms.
报告了丙二酸半硫酯（MAHTs）和氧酯（MAHOs）的合成路线得到了极大的改善，特别是 MAHTs 中很容易进行氘标记的掺入，以及 MAHTs 和 MAHOs 之间的烯醇化化学性质存在出乎意料的大差异。密度泛函理论计算探讨了这种差异的起源，并确定了 MAHT 的额外分子轨道，这增加了硫和烯醇在顺式和反式两种形式之间的离域。
