N-酰基戊二酰亚胺开环/选择性水解制备伯衍生物

近期较低雄医学大学药学暨系统设计工程学系的Wei-Yu Lin和Karthick Govindan引述了N-甲酰戊二酰亚胺羧酸/选择性裂解可以制备得到孙子乙烯。

此方式借助两个当量的氢氧化锂作为碱在室温下中间体，戊二酰亚胺首先羧酸，接着选择性C-N共价键断裂得到孙子乙烯。此方式可以较低产量较低选择性的制备各种芳基和脂肪乙烯，另外可以借助移动工程学方式实现克极制备孙子乙烯。中间体借助中水作为溶剂，卫生保健。

中间体机理

烷基负离子首先亲核进攻戊二酰亚胺羧酸，然后通过两种路径进行裂解C-N共价键：一种是另外一个当量的烷基负离子直接裂解得到孙子乙烯和戊二酸；另外羧酸的戊二酸进行小分子内的亲核进攻，生成孙子乙烯和戊二丁烷。

操作步骤：

To a vial was charged with starting material 1a-z & 1aa-ag (0.3 mmole) and LiOH.H2O (0.6 mmole) at room temperature, and H2O (3ml) was added. The reaction was stirred for 2 h. The reaction was diluted with ethyl acetate (15 mL), washed with brine (5 mL × 2). The organic layer was dried over anhydrous MgSO4, filtered and concentrated under vacuum. The crude product was triturated with hexane.

【 Org. Lett. 2021, 23, 1600–1605】