【摘要】 在光促进温和条件非贵金属催化下,实现了环氧化合物(环氧丙烷、1,2-环氧丁烷)与HCOOCH3的羰基化反应,合成得到了相应的β-羟基酸甲酯。通过对β-羟基丁酸甲酯和β-羟基戊酸甲酯的MS图分析,并与CH3OD或CD3OD代替CH3OH的同位素实验所得MS图的比较,说明HCOOCH3在光照下是先分解为CO和CH3OH后再与环氧化合物作用的,同时还证实β-羟基酸甲酯有两种氢参与McLafferty重排,即γ-H和β-OH中的H都可以参与McLafferty重排,且β-OH中的H参与的McLafferty重排比γ-H参与的McLafferty重排作用强。另外,当β-OH中的H由D取代后,更易进行McLafferty重排。更多还原

【Abstract】 The photo-promoted carbonylation of epoxides(propylene oxide,1,2-butylenoxide)with methyl formate was carried out under ambient conditions with non-precious metal catalysts.The corresponding methyl β-hydroxy acid esters were obtained.The main fragments of methyl β-hydroxybutyrate and methyl β-hydroxypentanoate were analyzed by MS.It was confirmed that HCOOCH3 first decomposed into CO and CH3OH under irradiation,followed by the photo-promoted carbonylation of the epoxide with CO and CH3OH.In addition,by comparison of the normal MS from CH3OH with the isotopic MS from CH3OD and CD3OD it was shown that two different hydrogen atoms,i.e.γ-H and H of β-OH,could participate in a McLafferty rearrangement.The abundance ratio of the relevant fragments indicated that transfer of the H of β-OH was favored over that of γ-H.In addition,the McLafferty rearrangement was favored when H of β-OH was replaced by D.更多还原