Synthesis of Primary gem-Dihydroperoxides and Their Peroxycarbenium [3 + 2] Cycloaddition Reactions with Alkenes
Synthesis of Primary gem-Dihydroperoxides and Their Peroxycarbenium [3 + 2] Cycloaddition Reactions with Alkenes
复制标题
初级偕二氢过氧化物及其过氧化碳鎓的合成[3 2]与烯烃的环加成反应
DOI：
10.1021/acs.joc.0c02180
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Yikang Wu
中科院分区：
文献类型：
--
作者：
Qinghong Zha;Yikang Wu
众所周知，脂肪醛的二氢过氧化是非常困难的，通常在羟基过氧化氢阶段中途停止。这种奇怪的现象现在已经被探索出来了，并且已经开发出一种高效的将脂肪醛转化为宝石二氢过氧化氢的协议。以2，6-二氢呋喃为碱实现了原宝石-二氢过氧化氢的硅基保护，这也是由于意外的碱诱导分解而带来的挑战。然后对硅基保护的GEM-二氢过氧化氢与烯烃的过氧卡宾[3+2]环加成反应进行了首次考察。芳香族底物通常反应平稳，得到预期的1，2-二氧杂环戊烷。脂肪醛一般不能生成1，2-二氧杂环戊烷。在所有情况下，根据所使用的烯烃，观察到意外地形成氯醇或1，2-二氯(氯原子来自TiCl4)，这显示了环加成反应的一些迄今未知的方面，并帮助获得了许多机械方面的见解。
It is long known that dihydroperoxidation of aliphatic aldehydes is extremely difficult and normally stops halfway at the hydroxyhydroperoxide stage. This strange phenomenon now has been explored, and a highly effective protocol for conversion of aliphatic aldehydes into gem-dihydroperoxides has been developed. Silyl protection of primary gem-dihydroperoxides, which is also a challenge due to unexpected based-induced decomposition, was achieved using 2,6-lutidine as the base. The silyl-protected gem-dihydroperoxides were then examined in a peroxycarbenium [3 + 2] cycloaddition reaction with alkenes for the first time. Aromatic substrates normally reacted smoothly, affording the expected 1,2-dioxolanes smoothly. Aliphatic aldehydes generally failed to yield 1,2-dioxolane. In all cases, unexpected formation of either a chlorohydrin or a 1,2-dichloride (with Cl atoms derived from TiCl4) depending on the alkene employed was observed, which displays some so far unknown facets of the cycloaddition and helped to gain many mechanistic insights.