Selenophosphoramide-catalyzed diamination and oxyamination of alkenes
Selenophosphoramide-catalyzed diamination and oxyamination of alkenes
复制标题
硒磷酰胺催化烯烃的二胺化和氧胺化
DOI：
10.1039/c9sc05335b
复制
发表时间：
2020
期刊：
影响因子：
8.4
通讯作者：
Michael, Forrest E.
中科院分区：
文献类型：
--
作者：
Tabor, John R.;Obenschain, Derek C.;Michael, Forrest E.
提出了一种新的硒磷酰胺催化末端和反式-1,2-二取代烯烃二化反应。这种转化成功的关键是引入了一种氟清除剂，三甲基硅基三氟甲烷磺酸盐（TMSOTf），以防止竞争性的syn消除途径，同时在硒上使用磷酰胺配体以促进所需的取代反应。催化剂的筛选表明，更多的富电子膦配体导致所需产品的产率更高，其中硒磷酰胺提供了最佳的结果。广泛的底物和官能团是耐受的，产量一般是好的。对于(E)-1,2-二取代烯烃，非对映选择性总是很高，得到的都是反产物。这些条件也适用于含有内亲核试剂的底物，如酯和碳酸盐，分别生成1,2-氨基酯和环状碳酸盐。
A new selenophosphoramide-catalyzed diamination of terminal- and trans-1,2-disubstituted olefins is presented. Key to the success of this transformation was the introduction of a fluoride scavenger, trimethylsilyl trifluoromethanesulfonate (TMSOTf), to prevent a competitive syn-elimination pathway, as was the use of a phosphoramide ligand on selenium to promote the desired substitution reaction. A screen of catalysts revealed that more electron-rich phosphine ligands resulted in higher yields of the desired product, with selenophosphoramides giving the optimal results. A broad range of substrates and functional groups were tolerated and yields were generally good to excellent. For (E)-1,2-disubstituted olefins, diastereoselectivities were always high, giving exclusively anti products. The conditions were also applied to substrates bearing internal nucleophiles such as esters and carbonates, giving rise to 1,2-aminoesters and cyclic carbonates, respectively.