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有机化学
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有机化学 ›› 2007, Vol. 27 ›› Issue (06): 739-743. 上一篇    下一篇

研究论文

重氮化合物与醇的插入反应合成α-烷氧基-β-二羰基化合物

黄丹a,b，鄢明*,c，沈琪*,b   

  1. (a江南大学化学与材料工程学院 无锡 214122)
    (b苏州大学化学化工学院 苏州 215006)
    (c中山大学药学院 广州 510080)
  • 收稿日期:2006-04-14 修回日期:1900-01-01 发布日期:2007-05-21
  • 通讯作者: 鄢明

Synthesis of α-Methoxyl-β-dicarbonyl Compounds by Insertion Reaction of Methanol to Diazo Compounds

HUANG Dana,b, YAN Ming*,c, SHEN Qi*,b   

  1. (a School of Chemical & Material Engineering, Southern Yangtze University, Wuxi 214122)
    (b College of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006)
    (c School of Pharmaceutical Sciences, Sun Yat-Sen University, Guangzhou 510080)
  • Received:2006-04-14 Revised:1900-01-01 Published:2007-05-21
  • Contact: YAN Ming

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研究了在过渡金属配合物催化下α-重氮-β-二羰基化合物与醇的插入反应, 考察了重氮化合物的结构、醇的结构、催化剂的性质、反应溶剂和反应温度对这一反应的影响. 发现当重氮化合物与甲醇的物质的量比为1∶10, 1 mmol% Rh2(OAc)4为催化剂和回流的苯的条件下, 反应能够以高的化学产率生成α-甲氧基-β-二羰基化合物. 手性醇衍生的重氮乙酰乙酸酯反应的产物中两种非对应异构体的比例为3∶2～1∶1.

关键词: 甲醇, 插入反应, Rh2(OAc)4, α-甲氧基-β-二羰基化合物, 重氮化合物

The paper studied catalyzed insertion reaction of α-diazo-β-dicarbonyl compounds into methanol and also investigated influence factors on the reaction, for example structures of diazo and alcohols, catalyst, solvent and reaction temperature. The best results were obtained with the use of 1 mmol of diazo, 10 mmol of methanol and 1 mmol% Rh2(OAc)4 as a catalyst in refluxing benzene. The reaction of diazoacetoacetic esters derived from chiral alcohols with methanol catalyzed by Rh2(OAc)4 provided chiral α-methoxyl-β-carbonyl esters in good yields and the diastereomer ratio of the product was 3∶2～1∶1.

Key words: insertion reaction, Rh2(OAc)4, α-methoxyl-β-dicarbonyl compound, methanol, diazo compound