Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates
Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates
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金催化磷酸烯丙酯、磷酸苄酯和磷酸丙酯的硫醚化反应
DOI：
10.1039/d1cy02085d
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发表时间：
2022
影响因子：
5
通讯作者：
Shishido Tetsuya
中科院分区：
文献类型：
--
作者：
Miura Hiroki;Toyomasu Tomoya;Nishio Hidenori;Shishido Tetsuya
金催化的C（sp3）-O键的硫醚化反应。烯丙基磷酸酯和硫代硅烷的反应中负载在ZrO 2上的金纳米粒子的存在下进行有效的温和的反应条件下，得到相应的烯丙基硫醚在优异的产率。ZrO2负载的金纳米粒子表现出优异的催化转化率和可重复使用性。此外，苄基和炔丙基磷酸酯的C-O键进行硫醚化，得到苄基和炔丙基硫化物。光学活性磷酸苄酯的反应进行了良好的手性转移，得到了高对映体纯度的苄基硫醚。控制实验证实，可溶性金物种负责磷酸盐的C-O键的有效硫醚化，和催化剂的表征显示，在表面的金纳米粒子负载在ZrO 2上的阳离子金物种作为高活性催化物种的来源。
Gold-catalyzed thioetherification of C(sp3)–O bonds is described. The reaction of allyl phosphates and thiosilanes in the presence of gold nanoparticles supported on ZrO2 proceeded efficiently under mild reaction conditions to give the corresponding allyl sulfides in excellent yields. ZrO2-Supported gold nanoparticles showed excellent catalytic turnover and reusability. In addition, the C–O bonds of benzyl and propargyl phosphates underwent thioetherification to afford benzyl and propargyl sulfides. The reaction of an optically active benzyl phosphate proceeded with excellent chirality transfer to give a benzyl sulfide with high enantiomeric purity. Control experiments corroborated that soluble gold species were responsible for the efficient thioetherification of C–O bonds of phosphates, and characterization of the catalysts revealed that cationic gold species at the surface of gold nanoparticles supported on ZrO2 served as a source for highly active catalytic species.