School of Chemistry and Chemical Engineering, Shanxi University , Taiyuan 030006, China.
Scientific Instrument Center, Shanxi University , Taiyuan 030006, China.
Org Lett. 2017 Nov 3;19(21):5798-5801. doi: 10.1021/acs.orglett.7b02753.
A new strategy to prepare β-acyl allylic methylsulfides and -sulfones through acid promoted direct cross-coupling of methyl ketones with dimethyl sulfoxide (DMSO) is reported. The reaction proceeded through the nucleophilic attack of enamine intermidiates derived from ketones to in situ generated thionium ion species, followed by elimination of methanthiol to give ketoallylic methylsulfides. With the prolonged reaction time, such products could be further reacted with a methyl sulfonyl radical, which might be generated from a methylthiosulfonate species, to afford ketoallylic methylsulfones in high yields. Molecular transformations of the allylic methylsulfides were also demonstrated.
本文报道了一种通过酸促进的甲基酮与二甲亚砜（DMSO）的直接交叉偶联来制备β-酰基烯丙基甲基硫醚和 - 亚砜的新策略。该反应通过来自酮的烯胺中间体对原位生成的硫翁离子物种的亲核攻击进行，然后消除甲硫醇得到酮烯丙基甲基硫醚。随着反应时间的延长，此类产物可以进一步与甲基磺酰基自由基反应，该自由基可能由甲基硫代硫酸盐物种生成，以高产率得到酮烯丙基甲基亚砜。还证明了烯丙基甲基硫醚的分子转化。
