Isolated Monomeric and Dimeric Mixed Diorganocuprates Based on the Size-Controllable Bulky "Rind" Ligands
Isolated Monomeric and Dimeric Mixed Diorganocuprates Based on the Size-Controllable Bulky "Rind" Ligands
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DOI：
10.1021/ja9071964
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发表时间：
2009-12-23
影响因子：
15
通讯作者：
Tamao, Kohei
中科院分区：
文献类型：
--
作者：
Ito, Mikinao;Hashizume, Daisuke;Tamao, Kohei
合成了可分离的混合二有机铜(I)配合物，并在熔融环八碳-r -取代的s-羟基癸烯骨架上引入了各种笨重的“Rind”基团，对其结构进行了表征。根据Rind配体的空间体积大小，用cur处理RindLi可生成有机溴铜二聚体[Cu(Rind)/ cur](2)或单体Li[Cu(Rind)Br]。随后，这些配合物中的溴原子被三甲基硅基乙酰锂取代，分别得到二聚体和单体芳基（炔基）铜(l)配合物A和B。配合物B是第一个可分离的混合双有机酸盐单体，被发现可以选择性地在铜上进行两个不同的有机基团的氧化交叉偶联。
Isotable mixed diorganocopper(I) complexes have been synthesized and structurally characterized by introducing a variety of bulky "Rind" groups based on a fused-ring octa-R-substituted s-hydrindacene skeleton. Treatment of RindLi with CuBr produced organobromocuprate dimers [Cu(Rind)/CuBr](2) or monomers Li[Cu(Rind)Br], depending on the steric bulkiness of the Rind ligands. Subsequent substitution of the bromine atoms in these complexes by lithium trimethylsilylacetylide gave dimeric and monomeric aryl(alkynyl)copper(l) complexes A and B, respectively. Complex B is the first isolable mixed diorganocuprate monomer formulated as LiCuRR' and was found to selectively undergo oxidative cross-coupling of two different organic groups on copper.