Yang Bing, Ji Xiaozhou, Xue Yunsheng, Zhang Haowei, Shen Minxing, Jiang Bo, Li Guigen
Institute of Chemistry and BioMedical Sciences and School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
Org Biomol Chem. 2016 Jul 7;14(25):6024-35. doi: 10.1039/c6ob00847j. Epub 2016 May 27.
Chiral N-phosphonyl imines have been proven to be efficient electrophilic acceptors for asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reactions with acrylates under convenient conditions. Thirty examples of β-amino acrylates were generated in high yields (up to 99.4%) and diastereoselectivity (up to >99 : 1 dr) in an atom-economical fashion. The synthesis was proved to follow the GAP (group-assisted purification) chemistry, i.e., the pure products can be obtained simply by washing the crude products with hexane/ethyl acetate (v/v, 10/1) without the use of chromatography or recrystallization. DFT calculations were also conducted to support an asymmetric induction model accounting for high diastereoselectivity.
手性N-膦酰亚胺已被证明是在便利条件下与丙烯酸酯进行不对称氮杂-Morita-Baylis-Hillman（氮杂-MBH）反应的有效亲电受体。以原子经济的方式高产率（高达99.4%）和非对映选择性（高达>99:1 dr）生成了30个β-氨基丙烯酸酯实例。该合成方法被证明遵循GAP（基团辅助纯化）化学，即仅通过用己烷/乙酸乙酯（v/v，10/1）洗涤粗产物即可获得纯产物，无需使用色谱法或重结晶。还进行了密度泛函理论（DFT）计算以支持解释高非对映选择性的不对称诱导模型。
