Palladium-catalyzed nucleophilic benzylic substitutions of benzylic esters

Palladium-catalyzed nucleophilic benzylic substitutions of benzylic esters
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DOI:
10.1021/ja037735z
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发表时间:
2003-10-08
影响因子:
15
通讯作者:
Matsuyama, Y
Matsuyama, Y
中科院分区:
化学1区
文献类型:
--
作者:
Kuwano, R;Kondo, Y;Matsuyama, Y

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由[Pd(η3-C3 H5)(cod)] BF 4和DPPF原位生成的钯配合物是碳酸苄甲酯与丙二酸二甲酯碳负离子苄基烷基化反应的良好催化剂。该催化反应适用于广泛的苄酯与丙二酸酯的苄基化反应。双齿膦配体在钯上的咬合角对催化活性有很大影响。DPEphos配体在钯催化苄基酯的苄基胺化反应中表现出上级的优越性。
A palladium complex generated in situ from [Pd(η3-C3H5)(cod)]BF4and DPPF is a good catalyst for benzylic alkylation of benzyl methyl carbonate with the carbanion of dimethyl malonates. The catalytic reaction is applicable to a wide range of the benzylations of benzylic esters with malonates. The catalytic activity was heavily affected by the bite angle of the bidentate phosphine ligand on palladium. DPEphos ligand is superior to DPPF in the case of palladium-catalyzed benzylic amination of benzylic esters.