188宝金博页面版

2011 文章编号: 0253-9837(2011)10-1573-04 Chinese Journal of Catalysis Vol. 32 No. 10 国际版 DOI: 10.1016/S1872-2067(10)60261-6 研究快讯: 1573~1576 手性磷酸催化芳香胺与硝基烯烃的不对称加成反应 杨 磊, 夏春谷, 黄汉民* 中 国 科学院兰州 化学物理研究所羰基合成与 选择氧化国 家重点实验室, 甘肃兰州 730000 摘要： 以轴手性联萘酚为原料, 合成了一系列手性磷酸催化剂, 并首次将其应用于催化芳香胺和硝基烯烃的不对称氮杂迈克尔加成反应中, 产物 β-硝基胺的产率和对映选择性分别达 65%~95% 和 16%~70%. 关键词： 手性磷酸; 芳香胺; 硝基烯烃; 氮杂迈克尔加成 中图分类号： O643 文献标识码： A 收稿日 期: 2011-07-07. 接受日 期: 2011-08-06. *通讯联系 人. 电话: (0931)4968326; 传真: (0931)4968129; 电子信箱: hmhuang@licp.cas.cn 基金来源: 国家自 然科学基金 (20802085). 本文的英文电子版(国际版)由Elsevier出 版社在ScienceDirect上出 版(http://www.sciencedirect.com/science/journal/18722067). Chiral Phosphoric Acid Catalyzed Enantioselective Aza-Michael Addition of Aromatic Amines to Nitroolefins YANG Lei, XIA Chungu, HUANG Hanmin* State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China Abstract: Chiral phosphoric acid was found to be an effective organocatalyst in the enantioselective aza-Michael addition of aromatic amines to nitroolefins giving the corresponding β-nitroamine products in good yields (65%–95%) with moderate to good enantiomeric ex-cesses (16%–70%). This study represents the first example of a chiral phosphoric acid catalyzed asymmetric aza-Michael addition reaction. Key words: chiral phosphoric acid; aromatic amine; nitroolefin; aza-Michael addition Received 7 July 2011. Accepted 6 August 2011. *Corresponding author. Tel: +86-931-4968326; Fax: +86-931-4968129; E-mail: hmhuang@licp.cas.cn This work was supported by the National Natural Science Foundation of China (20802085). English edition available online at Elsevier ScienceDirect (http://www.sciencedirect.com/science/journal/18722067). β-nitroamines are ubiquitous structural motifs found in biologically important natural products and pharmaceuti-cally active compounds, and they are also useful synthetic building blocks in organic synthesis especially for the syn-thesis of nitrogen-containing compounds [1]. Using well-established transformation β-nitroamines can be easily converted into α-amino acids or other α-aminocarbonyl compounds and vicinal diamines through the Nef reaction by the reduction of the nitro group [2]. Therefore, the development of an efficient synthetic method leading to β-nitroamines and their derivatives has attracted much attention in organic synthesis. Among the traditional methods used to generate β-nitroamines, the nu-chemistry, the cleophilic addition of nitroalkanes to imines and related compounds (aza-Henry or nitro-Mannich reaction) [3,4] is a powerful synthetic methodology that allows for the creation of two vicinal stereogenic centers bearing nitro and amino functional groups. Alternatively, because of its simplicity and atom economy the 1,4-addition of nitrogen nucleophiles to nitroolefins (aza-Michael reaction) is a convenient way to introduce this amine-based functionality to β-carbons that are attached to nitro groups (Scheme 1) [5–16]. Neverthe-less, compared with the former method for generating β-nitroamines, only a few reports of the corresponding aza-Michael addition of nitrogen reagents to nitroolefins have been documented in the literature wherein their