When ethyl is infinitely different from methyl: double addition of lithiated dithianes to aromatic carboxylates revisited.
When ethyl is infinitely different from methyl: double addition of lithiated dithianes to aromatic carboxylates revisited.
复制标题
当乙基与甲基无限不同时：重新审视锂化二噻烷与芳香族羧酸盐的双重加成。
DOI：
10.1021/jo060780f
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
Kutateladze,AndreiG
中科院分区：
文献类型：
--
作者：
Valiulin,RomanA;Kottani,Rudresha;Kutateladze,AndreiG
Addition of lithiated alkyl dithianes to benzoyl chloride or methyl benzoate does not produce the expected product of double addition, α,α-bis(alkyldithianyl) benzyl alcohol, for alkyls larger than methyl. Instead, the first step intermediate, i.e. 2-benzoylated dithiane, undergoes an electron-transfer reduction by the second molecule of the dithianyl anion. This reduction is followed by the ring-opening mesolytic fragmentation of the dithiane ring in the ketyl anion radical and subsequent radical recombination yielding acetophenone-tethered thioortho esters4, α-[3-(2-alkyl-1,3-dithiane-2-ylthio)propylthio]-α-alkyl-acetophenones. It appears that the Corey−Seebach bisaddition of lithiated dithianes to methyl benzoate is an exception rather than the rule in the alkyl dithiane series.
