Organocatalytic Kinetic Resolution of Racemic Secondary Nitroallylic Alcohols Combined with Simultaneous Desymmetrization of Prochiral Cyclic Anhydrides

This study describes an organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols (2) combined with simultaneous desymmetrization of prochiral cyclic anhydrides (1). The experimental results revealed that enantioselective alcoholysis of 3-substituted glutaric anhydrides afforded hemiesters (3) with high levels of enantioselectivities (up to 99% ee) in the presence of cinchonidine-derived thiourea catalyst (IV). The highly optical enrichment (up to 95% ee) of (S)-nitroallylic alcohols (2) was recovered.

本研究报道了一种有机催化动力学拆分（organocatalytic kinetic resolution）策略，用于对外消旋二级硝基烯丙醇（2）进行拆分，并同时实现前手性环状酸酐（1）的去对称化（desymmetrization）。实验结果表明，在辛可宁衍生的硫脲催化剂（cinchonidine-derived thiourea catalyst，IV）存在下，对3-取代戊二酸酐（3-substituted glutaric anhydrides）进行对映选择性醇解（enantioselective alcoholysis），可得到半酯（hemiesters，3），其对映选择性水平优异，最高可达99% ee。同时可回收得到光学富集度优异（最高可达95% ee）的(S)-硝基烯丙醇（2）。