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有机化学 ›› 2008, Vol. 28 ›› Issue (08): 1410-1415. 上一篇    下一篇

研究论文

大位阻、富电子MOP型烷基膦配体在钯催化的1,3-二羰基化合物 α-芳基化反应中的应用

江 洪a; 马芳芳a ; 谢小敏a ; 张兆国*,a,b   

  1. (a上海交通大学化学化工学院 上海 200240)
    (b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)
  • 收稿日期:2008-01-14 修回日期:2008-04-01 发布日期:2008-08-18
  • 通讯作者: 张兆国

Application of Bulky and Electron-Rich MOP-Type Phosphine Ligands in Palladium-Catalyzed α-Arylation of 1,3-Dicarbonyl Compounds

JIANG, Hong a; MA, Fang-Fang a; XIE, Xiao-Mina ; ZHANG, Zhao-Guo*,a,b   

  1. (aSchool of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240)
    (bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
    Chinese Academy of Sciences, Shanghai 200032)
  • Received:2008-01-14 Revised:2008-04-01 Published:2008-08-18
  • Contact: ZHANG, Zhao-Guo

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2

富电子、大位阻MOP型烷基膦配体2-二叔丁基膦-2’-异丙氧基-1,1’-联萘(L1)在钯催化的1,3-二羰基化合物的α-芳基化反应中显示了较好的催化活性. 在这类催化反应中, 碱的选择具有重要的影响: 以K3PO4为碱, Pd(OAc)2/L1催化体系在丙二酸二乙酯的α-芳基化中, 富电子溴代芳烃显示较好的活性; Pd(OAc)2/L1催化的乙酰乙酸乙酯α-芳基化时, 以 K2CO3为碱, 催化体系显示较好的活性, 这个催化体系可控制反应得到α-芳基乙酰乙酸乙酯, 而不是脱乙酰基的产物. 较为惰性的氯代芳烃在Pd(OAc)2/L1的催化下, 也能够跟1,3-二羰基化合物发生α-芳基化反应.

关键词: 钯催化, α-芳基化, 膦配体, 卤代芳烃

Bulky and electron-rich MOP-type phosphine ligand 2-ditertbutylphosphino-2’-isopropyloxy-　1,1’-binaphthyl (L1) shows good catalytic activity in palladium-catalyzed α-arylation of 1,3-dicarbonyl compounds. Base played a crucial role in this reaction: in the Pd(OAc)2/L1 catalyzed α-arylation of ethyl malonate, K3PO4 is the base of choice; in the α-arylation of ethyl acetoacetate, K2CO3 is the most effective base. For the α-arylation of ethyl acetoacetate, the product was α-aryl ethyl acetoacetates, rather than ethyl α-arylacetates which are the major products in other catalytic systems.

Key words: palladium-catalysis, aryl halide, phosphine, α-arylation