Expanding Ligand Space: Preparation, Characterization, and Synthetic Applications of Air-Stable, Odorless Di-<i>tert</i>-alkylphosphine Surrogates
作者:Thomas Barber、Stephen P. Argent、Liam T. Ball
DOI:10.1021/acscatal.0c01414
日期:2020.5.15
catalysis. However, the structural diversity of these privileged substructures is currently limited by the need to manipulate highly toxic, highly reactive reagents and intermediates in their synthesis. In response to this longstanding challenge, we report an umpolung strategy for the synthesis of structurally diverse di-tert-alkylphosphine building blocks via SN1 alkylation of in situ generated PH3
对于后过渡金属催化,许多同类最佳配体都具有二叔烷基膦基序。但是,这些特权亚结构的结构多样性目前受到在合成过程中操纵高毒性,高反应性试剂和中间体的需求的限制。在响应于这一长期挑战,我们报告了结构不同的二-合成中的极性转换策略叔通过S -烷基积木Ñ 1个烷基化的原位产生的PH 3分的气体。我们证明了作为空气稳定,无味的phospho盐分离出的产品,可以直接用于制备关键的合成中间体和配体类别。二-叔因此,使用我们的方法学可获得的-烷基膦基结构单元可通过修饰先前不变的载体轻松扩展现有的配体类别;我们证明这些修饰会影响配体的空间和电子性质,并可用于调整其催化性能。