Catalytic coupling of terminal alkynes with isonitriles promoted by organoactinide complexes
Catalytic coupling of terminal alkynes with isonitriles promoted by organoactinide complexes
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DOI：
10.1021/ja046604a
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发表时间：
2004-09-08
影响因子：
15
通讯作者：
Eisen, MS
中科院分区：
文献类型：
--
作者：
Barnea, E;Andrea, T;Eisen, MS
在有机锕系中性配合物Cp* 2AnMe 2（Cp* = C5 Me 5，An = Th，U）和阳离子配合物[（Et 2N）3U][BPh 4]的催化下，端炔与叔丁基异腈偶联生成取代α，β-炔醛亚胺。该反应通过异腈1，1-插入金属-乙炔键进行。通过改变催化剂和反应物的比例，可以获得额外的插入产物。除了Cp* 2UMe 2的晶体结构外，还提出了催化反应的合理机理
The coupling reaction of terminal alkynes andtert-butylisonitrile to yield substituted α,β-acetylenic aldimines is catalyzed by the organoactinide neutral complexes Cp*2AnMe2(Cp* = C5Me5, An = Th, U) and the cationic complex [(Et2N)3U][BPh4]. The reaction proceeds by a 1,1-insertion of the isonitrile into the metal−acetylide bond. Additional insertion products can be obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is presented, in addition to the crystal structure of Cp*2UMe2