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有机催化吡唑酮与MBH碳酸酯的不对称烯丙基烷基化反应
Organocatalyzed Asymmetric Allylic Alkylation of MBH-Carbonates with Pyrazolones

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马世雄 1   钟源 1   王守磊 1   许兆青 2 *   常民 1   王锐 3 *  
文摘 报道了辛可宁催化的MBH (Morita-Baylis-Hillman)碳酸酯β位和吡唑酮的不对称烯丙基烷基化反应.在温和的条件下,此反应以良好的产率(55%~91%)和最高93%的对映选择性得到了一系列手性吡唑酮类化合物.
其他语种文摘 The asymmetric allylic alkylation (AAA) reaction is one of the important transformations in asymmetric synthesis, which was intensively studied in the last decade. Recently, the use of Morita-Baylis-Hillman (MBH) carbonates as electrophiles for the AAA reaction has attracted much attention. Pyrazole is an important pharmacophore, which often exhibit various biological and pharmacological activities. In the last years, the asymmetric synthesis using pyrazolones as the nucleophiles were reported by several research groups. However, the work were mainly focused on the asymmetric conjugate addition of pyrazoles to α,β-unsaturated compounds, and other types of enantioselective reactions were seldom studied. Herein, we report the first example of AAA reaction of MBH carbonates using pyrazolones as nucleophiles. In the reaction, we found that different Lewis basic catalyst, namely PPh_3 and DABCO, shown different regioselectivity: PPh_3 gave the γ-selective product whereas DABCO led to a complete β-selectivity. During the catalyst screening, cinchonine gave the best result. The enantioselectivity heavily relied on the choice of solvent: MeOH was superior compared to EtOH, CH_2Cl_2, DCE, acetone, CH_3CN, toluene, m-xylene and PhCl. In the substrate scope study, all the reactions were proceeded smoothly under mild conditions by using cinchonine as the catalyst (20 mol%) and give the β-selective allylic alkylation products with good yields (55%~91%) and high enantioselectivities (up to 93% ee). Based on our experimental results and previous reports, a preliminary mechanism of bifunctional catalysis was proposed. A representative procedure for the asymmetric allylic alkylation of MBH-carbonates with pyrazolones is as follows: to a flask equipped with a magnetic stirring bar was charged with pyrazolone 1 (0.1 mmol) and MBH-carbonate 2 (0.12 mmol) in methanol (2 mL), and then, the cinchonine catalyst (6 mg, 20 mol%) was added under air. The reaction solution was stirred at room temperature for 72 to 96 hours. Then, the mixture was concentrated and purified through a flash chromatography (silica gel, PE/EtOAc, V∶V=7∶1) to give the corresponding products 3.
来源 化学学报 ,2014,72(7):825-829 【核心库】
DOI 10.6023/a14040319
关键词 有机催化 ; 辛可宁 ; MBH碳酸酯 ; 吡唑酮 ; 不对称烯丙基烷基化
地址

1. 兰州大学生命科学学院, 兰州, 730000  

2. 兰州大学, 甘肃省新药临床前研究重点实验室, 兰州, 730000  

3. 兰州大学生命科学学院, 甘肃省新药临床前研究重点实验室, 兰州, 730000

语种 中文
文献类型 研究性论文
ISSN 0567-7351
学科 化学;化学工业
基金 国家自然科学基金 ;  中央高校基础研究基金
文献收藏号 CSCD:5204049

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引证文献 3 篇

1 丁正伟 铜促进下腙的氧化胺化反应:1H-吲唑和1H-吡唑的合成 化学学报,2015,73(12):1302-1306
被引 4 次

2 周霄乐 1,4-二烯和醛的烯丙基碳氢不对称烷基化反应 化学学报,2018,76(11):857-861
被引 2 次

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