Palladium-iminophosphine-catalyzed alkynylstannylation of alkynes
Palladium-iminophosphine-catalyzed alkynylstannylation of alkynes
复制标题
钯亚氨基膦催化的炔烃的炔基甲锡烷基化
DOI：
10.1021/om000828u
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发表时间：
2000
期刊：
影响因子：
2.8
通讯作者：
T. Hiyama
中科院分区：
文献类型：
--
作者：
H. Yoshida;E. Shirakawa;T. Kurahashi;Y. Nakao;T. Hiyama
由亚氨基膦配体配位的钯络合物被发现催化炔基锡烷加成到各种炔的碳碳三键上，产率中等至良好，具有独特的顺式选择性。除了1-炔-3-酮和炔酸酯外，锡烷中的炔基主要连接在末端炔的内碳上。配体的空间体积对反应的区域选择性和反应速率有显著的影响：具有较大亚氨基部分的亚氨基膦加速了炔基锡烷基化反应，具有较高的区域选择性。在此基础上，对反应机理进行了讨论。
A palladium complex coordinated by an iminophosphine ligand was found to catalyze the addition of alkynylstannanes to a carbon−carbon triple bond of various alkynes in moderate to good yields with exclusive syn selectivity. The alkynyl group in the stannanes was attached mainly to the internal carbon of terminal alkynes, except for 1-alkyn-3-ones and alkynoates, where the alkynyl group was connected to the terminal carbon. Steric bulk of the ligand markedly influenced on the regioselectivity and reaction rate: an iminophosphine with a bulkier imino moiety accelerated the alkynylstannylation with higher regioselectivity. On the basis of these observations, the mechanism of the present reaction is discussed.