双齿氮配体钯配合物催化的羰化反应研究

Carbonylation with the New Nitrogen Bidentate Palladium Catalysts

研究了双齿氮配体钯(II)配合物催化剂(1-3)在对邻溴碘苯与胺的羰化合成酰胺反应以及炔烃的氧化羰化制备炔酸酯反应中的催化性能,考察了不同条件下催化剂的催化活性并对其反应产物进行了表征.研究结果表明该催化剂在酰胺化合成氮取代邻苯二甲酰亚胺的反应中表现出了较好的催化活性和选择性,分离收率和选择性高达88%和85%;在芳基炔烃的氧化羰化反应中也得到最高83%的炔酸酯分离收率,但对杂环类炔烃的催化活性较低.这种无磷催化剂为合成氮取代邻苯二甲酰亚胺和炔酸酯提供了一种理想途径.

The palladium（II） complex（1-3） with bidentate nitrogen ligand demonstrated high catalytic activities in the carbonylation of 1-bromo-2-iodobenzene and amine to yield N-substituted phthalimides（5） with up to 88% isolated yield at mild conditions.It was also active toward the oxidative carbonylation of aryl acetylene affording methyl phenylpropiolate（6） with an isolated yield as high as 83% at room temperature and low CO pressure,but to the heterocycle alkyne the catalyst indicated low activity.The present phosphine-free catalytic system provides an ideal alternative for the direct synthesis of N-substituted phthalimides and methyl phenylpropiolate.