Asymmetric aza-Morita–Baylis–Hillman reactions of chiral N-phosphonyl imines with acrylates via GAP chemistry/technology. Issue 25 (27th May 2016)

• Record Type: Journal Article
• Authors: Yang, Bing; Ji, Xiaozhou; Xue, Yunsheng; Zhang, Haowei; Shen, Minxing; Jiang, Bo; Li, Guigen
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 25(2016)
• Page Start: 6024
• Page End: 6035
• Publication Date: 2016-05-27
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob00847j
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : A series of aza-Morita–Baylis–Hillman acrylates have been synthesized by using chiral N -phosphonyl imines and GAP chemistry/technology. Abstract : 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.