Park Jin Hyun, Maity Pintu, Paladhi Sushovan, Bae Han Yong, Song Choong Eui
Department of Chemistry, Sungkyunkwan University, Suwon, 16419, Korea.
Department of Chemistry, Thakur Prasad Singh (T.P.S.) College, Patna, 800001, India.
Chemistry. 2023 Sep 15;29(52):e202301787. doi: 10.1002/chem.202301787. Epub 2023 Aug 10.
Chiral allylic amines are valuable building blocks for biologically important compounds and natural products. In this study, we present the use of cooperative cation-binding catalysis as an efficient method for synthesizing chiral allylic amines. By utilizing a chiral oligoEG and potassium fluoride as a cation-binding catalyst and base, respectively, a wide range of biologically relevant chiral 2-nitroallylic amines are obtained with excellent enantioselectivities (up to >99 % ee) through the organocatalytic asymmetric aza-Henry-like reaction of β-monosubstituted and β,β-disubstituted nitroalkenes with α-amidosulfones as imine precursors. Extensive experimental studies are presented to illustrate plausible mechanisms. Preliminary use of a chiral 2-nitroallylic amine as a Michael acceptor demonstrated its potential application for diversity-oriented synthesis of bioactive compounds.
手性烯丙基胺是用于合成具有生物学重要性的化合物和天然产物的重要结构单元。在本研究中，我们展示了利用协同阳离子结合催化作为合成手性烯丙基胺的有效方法。通过分别使用手性低聚乙二醇和氟化钾作为阳离子结合催化剂和碱，通过β-单取代和β,β-二取代硝基烯烃与α-氨基砜作为亚胺前体的有机催化不对称氮杂-Henry类反应，以优异的对映选择性（高达>99% ee）获得了一系列与生物学相关的手性2-硝基烯丙基胺。本文还进行了广泛的实验研究以阐明可能的反应机理。将手性2-硝基烯丙基胺初步用作迈克尔受体，证明了其在生物活性化合物的多样性导向合成中的潜在应用。
