Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (8): 2328-2332.DOI: 10.6023/cjoc201902036 Previous Articles     Next Articles

Special Issue: 陈茹玉先生诞辰100周年

Notes

Rh2(OAc)4催化的Wittig-Type烯基化反应:一种合成烷基、芳基取代的亚烷基丙二酸酯的简便方法

邓超a,b, 周姣龙a, 刘华魁a, 王丽佳c, 唐勇a   

  1. a 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032;
    b 南京农业大学理学院 江苏省农药学重点实验室 南京 210095;
    c 华东师范大学化学与分子工程学院 上海 200241
  • 收稿日期:2019-02-28 修回日期:2019-04-12 出版日期:2019-08-25 发布日期:2019-05-06
  • 通讯作者: 周姣龙, 王丽佳 E-mail:ljwang@chem.ecnu.edu.cn;jolorsh@sioc.ac.cn
  • 基金资助:

    国家自然科学基金(Nos.21432011,21772224)、中国科学院前沿重点项目(No.QYZDY-SSW-SLH016)、中国科学院先导项目(No.XDB20000000)、上海市自然科学基金(No.17ZR1436900)、南京农业大学启动经费(No.050-804099)资助项目.

Rh2(OAc)4 Catalyzed Wittig-Type Olefination: A Facile Access to Alkylidene and Arylidene Malonates

Deng Chaoa,b, Zhou Jiaolonga, Liu Huakuia, Wang Lijiac, Tang Yonga   

  1. a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
    b Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing 210095;
    c School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241
  • Received:2019-02-28 Revised:2019-04-12 Online:2019-08-25 Published:2019-05-06
  • Contact: 10.6023/cjoc201902036 E-mail:ljwang@chem.ecnu.edu.cn;jolorsh@sioc.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21432011, 21772224), the Key Research Program of Frontier Sciences of Chinese Academy of Sciences (No. QYZDY-SSW-SLH016), the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB20000000) and the Natural Science Foundation of Shanghai City (No. 17ZR1436900), and the Start-up Research Fund of Nanjing Agricultural University (No. 050-804099).

In the presence of triphenylarsine and catalytic amount of Rh2(OAc)4, one pot reactions with carbonyl compounds and dimethyl diazomalonate give the corresponding alkylidene and arylidene malonates in moderate to excellent yields (59%~99%). The scope of the carbonyl compounds covered a broad range, including aromatic and aliphatic aldehydes and ketone. The reaction was easily scaled up to gram scale with 0.5 mol% rhodium catalyst loading. The preliminary mechanistic studies showed that the olefination proceeded via a rhodium-carbene transformed arsonium ylide pathway.

Key words: diazo compounds, alkylidene malonates, rhodium, triphenylarsine, Wittig reaction