Scalable Synthesis of Enantiopure Bis-3,4-diazaphospholane Ligands for Asymmetric Catalysis

An optimized route to enantiopure tetra-carboxylic acid and tetra-carboxamide bis­(diaza­phospholane) ligands that obviates chromatographic purification is presented. This synthesis, which is demonstrated on 15 and 100 g scales, features a scalable classical resolution of tetra-carboxylic acid enantiomers with recycling of the resolving agent. When paired with a rhodium metal center, these bis­(diaza­phospholane) ligands are highly active and selective in asymmetric hydroformylation applications.

本研究报道了一条无需色谱纯化即可获得对映纯四羧酸与四甲酰胺双(二氮杂磷杂环戊烷)配体(bis(diazaphospholane) ligands)的优化合成路线。该合成已在15 g与100 g规模下得到验证，其核心特点为可通过拆分剂回收实现四羧酸对映体的可放大经典拆分。将此类双(二氮杂磷杂环戊烷)配体与铑金属中心配位后，其在不对称氢甲酰化应用中表现出优异的活性与选择性。