Mild reductions of oxides of the Group 6a elements sulfur, selenium, and tellurium with (phenylseleno)trimethylsilane
Mild reductions of oxides of the Group 6a elements sulfur, selenium, and tellurium with (phenylseleno)trimethylsilane
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用(苯基硒基)三甲基硅烷温和还原 6a 族元素硫、硒和碲的氧化物
DOI：
10.1021/jo00393a015
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发表时间：
1979
期刊：
影响因子：
--
通讯作者：
M. Detty
中科院分区：
文献类型：
--
作者：
M. Detty
结果 当尝试用催化量的氟化钾、2 氰化钾、2 甚至三苯基膦 3 将 1 加成到某些酮或 β-不饱和羰基化合物上，但没有取得普遍成功时，我们尝试在 1 和二甲亚砜 (Me2SO) 之间生成诸如 2 的络合物。对这种配合物的一个希望是，苯基硒化物阴离子的亲核攻击将导致氧阴离子与锍物种的甲硅烷基化。当将 1 添加到 Me2SO 中时，立即发生放热反应，并从反应容器中蒸馏出二甲基硫醚。可以从反应混合物中分离出二苯基二硒化物和六甲基二硅氧烷。在氯仿中，2 当量的 1 与 1 当量的 Me2SO 反应，得到二甲基硫醚 (98%)、二苯基二硒化物 (95% 分离) 和六甲基二硅氧烷 (90%)。第四种产物以 2% 的产率分离出来，并根据光谱证据被指定为结构 3。核磁共振
Results When attempts to add 1 to certain ketones or to, ß-unsaturated carbonyl compounds with catalytic amounts of potassium fluoride, 2 potassium cyanide, 2 or even tri-phenylphosphine3 did not meet with general success, we attempted to generate a complex such as 2 between 1 and dimethyl sulfoxide (Me2SO). One hope for such a complex was that nucleophilic attack by the phenylselenide anion would be followed by silylationof an oxygen anion with the sulfonium species.When 1 was added to Me2SO, an immediate exothermic reaction occurred and dimethyl sulfide distilled from the reaction vessel. Diphenyl diselenide and hexamethyl-disiloxane could be isolated from the reaction mixture. In chloroform, 2 equiv of 1 reacted with 1 equiv of Me2SO to give dimethyl sulfide (98%), diphenyl diselenide (95% isolated), and hexamethyldisiloxane (90%). A fourth product was isolated in 2% yield and was assigned structure 3 based on spectral evidence. The NMR