Homo- and heterodehydrocoupling of phosphines mediated by alkali metal catalysts
Homo- and heterodehydrocoupling of phosphines mediated by alkali metal catalysts
复制标题
DOI：
10.1038/s41467-019-09832-4
复制
发表时间：
2019-06-26
影响因子：
16.6
通讯作者：
Manners, Ian
中科院分区：
文献类型：
--
作者：
Wu, Lipeng;Annibale, Vincent T.;Manners, Ian
涉及主基团底物的活化和转化的催化化学相对不发达，目前的例子通常是由昂贵的过渡金属物质介导的。在这里，我们描述了使用廉价和容易获得的tBuOK作为P-P和P-E （E = O， S或N）键形成的催化剂。在亚胺、偶氮苯氢受体存在下的催化量，或在化学计量量的偶氮苯存在下的催化量，允许在温和的条件下（例如25摄氏度和< 5分钟）实现磷化氢的高效脱氢偶联。进一步的研究表明，氢受体起着密切的机制作用。我们还表明，我们的tBuOK催化方法适用于膦与醇、硫醇和胺的异氢脱氢偶联，以产生一系列含有P-O、P-S或P-N键的潜在有用产物。
Catalytic chemistry that involves the activation and transformation of main group substrates is relatively undeveloped and current examples are generally mediated by expensive transition metal species. Herein, we describe the use of inexpensive and readily available tBuOK as a catalyst for P-P and P-E (E = O, S, or N) bond formation. Catalytic quantities of tBuOK in the presence of imine, azobenzene hydrogen acceptors, or a stoichiometric amount of tBuOK with hydrazobenzene, allow efficient homodehydrocoupling of phosphines under mild conditions (e.g. 25 degrees C and < 5 min). Further studies demonstrate that the hydrogen acceptors play an intimate mechanistic role. We also show that our tBuOK catalysed methodology is general for the heterodehydrocoupling of phosphines with alcohols, thiols and amines to generate a range of potentially useful products containing P-O, P-S, or P-N bonds.