Du Da-Ming, Fang Tao, Xu Jiaxi, Zhang Shi-Wei
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
Org Lett. 2006 Mar 30;8(7):1327-30. doi: 10.1021/ol0600584.
[reaction: see text] A series of new chiral C(3)-symmetric tris(beta-hydroxy phosphoramide) ligands have been synthesized via the reaction of trisphosphoramide ester and Grignard reagents. The catalytic asymmetric borane reduction of ketones with these new C(3)-symmetric chiral tris(beta-hydroxy phosphoramide)s was investigated. Structurally well-defined, recoverable ligand 1d is an efficient catalyst for the enantioselective borane reduction of both electron-deficient and electron-rich ketones, and high enantioselectivities were achieved (up to 98% ee).
[反应：见正文] 通过三磷酰胺酯与格氏试剂的反应合成了一系列新型手性C(3)对称三(β-羟基磷酰胺)配体。研究了用这些新型C(3)对称手性三(β-羟基磷酰胺)对酮进行催化不对称硼烷还原反应。结构明确、可回收的配体1d是一种高效催化剂，可对缺电子和富电子酮进行对映选择性硼烷还原，且能实现高对映选择性（高达98% ee）。
