On-demand, in situ , generation of ammonium caroate (peroxymonosulfate) for the dihydroxylation of alkenes to vicinal diols
On-demand, in situ , generation of ammonium caroate (peroxymonosulfate) for the dihydroxylation of alkenes to vicinal diols
复制标题
按需原位生成胡萝卜酸铵（过一硫酸盐），用于将烯烃二羟基化为邻位二醇
DOI：
10.1039/d2gc00671e
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发表时间：
2022
期刊：
影响因子：
9.8
通讯作者：
Deadman B
中科院分区：
文献类型：
--
作者：
Deadman B
使用烯烃的二羟基化作为基准，将新鲜和老化的（NH4）2S2 O8溶液（电化学产生）的反应性与商业采购的过硫酸盐和过硫酸氢钾进行比较。研究表明，过氧单硫酸盐（卡罗酸，PMS）是这种反应中的活性氧化剂。使用互补氧化还原比色法和原位红外光谱，分解过二硫酸盐在酸性溶液中到PMS和H2O2可以量化的第一次。新的见解使间歇和流动工艺的设计和实施能够最大限度地提高活性PMS氧化剂的浓度。这些氧化剂用于有机合成的效用通过八种苯乙烯和七种烷基烯烃的二羟基化来证明，其中铵PMS溶液的性能优于过硫酸氢钾溶液（对抗效应）。最后但并非最不重要的是，开发了用于分离和纯化水溶性二醇产物的无色谱方法。
Using the dihydroxylation of alkenes as a benchmark, the reactivities of fresh and aged solutions of (NH4)2S2O8 (electrochemically generated) were compared to commercially-procured peroxydisulfate and Oxone. The study revealed that peroxymonosulfate (Caro's acid, PMS) is the active oxidant in such reactions. Using complementary redox colorimetry and in situ IR spectroscopy, the decomposition of peroxydisulfate in an acidic solution into PMS and H2O2 can be quantified for the first time. The new insights enabled the design and implementation of both batch and flow processes to maximise the concentration of active PMS oxidant. The utility of these oxidants for organic synthesis is demonstrated by the dihydroxylation of eight styrenes and seven alkyl alkenes, where the ammonium PMS solutions performed better than Oxone (counterion effect). Last but not least, a chromatography-free method for isolating and purifying the water-soluble diol product was developed.