外消旋烷氧基膦-硼烷的立体选择性转化为 -手性叔膦 P-O 键的断裂。

The stereoselective conversion of epimerized alkoxyl phosphine-borane to -stereogenic tertiary phosphine cleavage of P-O bond.

机构信息

College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong 252059, China.

出版信息

Org Biomol Chem. 2022 Mar 30;20(13):2615-2620. doi: 10.1039/d2ob00351a.

Abstract

The P-O bond of epimerized alkoxyl phosphine-borane was cleaved by naphthalene-lithium, to form two diastereomers of P-anions in a ratio of 86 : 14, which was then converted to secondary phosphine-borane acidification, and to tertiary phosphines with alkyl halides with enhanced 96 : 4 dr. The isolated tertiary phosphine containing hydroxyl (in >99 : 1 dr) was converted to multi-stereogenic tertiary phosphines -alkylation with alkylene dihalides.

摘要

萘锂引发差向异构化的烷氧基膦-硼烷的 P-O 键断裂，形成两种非对映异构体 P-阴离子，比例为 86 : 14，然后将其转化为仲膦-硼烷酸，再与卤代烃反应得到三级膦，非对映选择性提高到 96 : 4。分离出的含有羟基的三级膦（>99 : 1 dr）可与二卤代亚烷基反应，进一步转化为多手性三级膦-烷基化产物。