化学学报 ›› 1988, Vol. 46 ›› Issue (11): 1113-1118. 上一篇    下一篇

研究论文

钯催化烯丙基偕二醇二醋酸酯和各种亲核试剂的反应

黄煜津;陆熙炎   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1988-11-15

Palladium catalyzed reaction of allylic geminal diacetates with nucleophiles

HUANG YUJIN;LU XIYAN   

  • Published:1988-11-15

研究了配体对烯丙基-1,1-偕二醇二醋酸酯(1)在钯配合物催化下和丙二酸酯钠盐反应的影响. 当用PPh3为配位体时, 丙二酸酯碳阴离子进攻在羰基碳上, 当用dppe为配体时, 进攻在烯丙基碳上. 亲核试剂的性质也影响反应进攻的位置. 通过选择适当的亲核试剂和配体可以从1得到二次烷基化的产物.

关键词: 乙酸酯, 催化, 羧酸酯, 醇, 三苯基膦, 丙二酸 P, 亲核反应, 化学试剂, 钯络合物, 烯丙基

The influence of ligands on the palladium catalyzed reaction of allylic-1,1-diol diacetate RCH:CHCH(OAc)2 (I, R = H, Me, Ph) with di-Me sodiomalonate anion was studied. When PPh3 was used as the ligand, the malonate anion was found to attack the carbonyl carbon atom, but it would attack the allylic carbon atom while 1,2-bis(diphenylphosphino)ethane was used as the ligand. The properties of nucleophiles also influence the position of attack. By suitable choice of the nucleophiles and ligands, dialkylated products can be obtained from I.

Key words: ACETIC ACID ESTER, CATALYSIS, CARBOXYLIC ACID ESTER, ALCOHOL, TRIPHENYLPHOSPHINE, MALONIC ACID P, NUCLEOPHILIC REACTION, CHEMICAL REAGENT, PALLADIUM COMPLEX, ALLYL GROUP

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