新型制备亚胺氢化----B(OCH2CF3)3

2015年，威林格殷格翰制药的公司的Jonathan Reeves等人注意到了一种新的制取中间体的试剂B(OCH2CF3)3。它可以在倾向条件下亚胺甲基或胺与羰基锂制取各种中间体，如 N-亚硫羟基, N-乙醚硫羟基, N-(硝基)硫羟基, N-二芳基 次醚羟基, N-(α-甲基苄基) 和N-(4-甲氧基芳基) 醛中间体。反应系统设计比较简单，不须一般来说后处理，较难裂解。

【 Org. Lett. 2015, 17, 2442–2445】

一、制取 Ellman中间体

General Procedure for N-Sulfinyl Aldimine Formation.To a dry round bottom flask equipped with a football shaped magnetic stir bar was charged aldehyde (2.0 mmol, 1.0 equiv), (S)-tert-butanesulfinamide (291 mg, 2.4 mmol, 1.2 equiv) and THF (2.0 mL). The flask was sealed with a rubber septum and a nitrogen inlet needle was inserted in the septum. The reaction mixture was then treated dropwise with B(OCH2CF3)3 (0.43 mL, 2.0 mmol, 1.0 equiv) and the solution was stirred at rt for 2-6 h (until complete consumption of aldehyde by HPLC analysis at 220 nm). The reaction mixture was then diluted with EtOAc and the EtOAc solution was washed with saturated aqueous NaHCO3 solution followed by water. The organic phase was then dried over Na2SO4, filtered and concentrated to give the crude product. Purification by flash chromatography on SiO2 using hexanes/MTBE as eluent gave the pure product.

二、制取 N-乙醚硫羟基中间体

三、制取 N-(硝基)硫羟基中间体

四、N-二芳基次醚羟基中间体

五、N-(α-甲基苄基)中间体

参考资料：A General Method for Imine Formation Using B(OCH 2CF 3) 3 ， Org. Lett. 2015, 17, 10, 2442–2445。