Dimerization–Carbostannylation of Alkynes Catalyzed by a Palladium–Diimine Complex: Regioselectivity, Stereoselectivity and Mechanism
Dimerization–Carbostannylation of Alkynes Catalyzed by a Palladium–Diimine Complex: Regioselectivity, Stereoselectivity and Mechanism
复制标题
钯-二胺配合物催化炔烃的二聚-碳锡烷基化：区域选择性、立体选择性和机理
DOI：
10.1246/bcsj.74.637
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发表时间：
2001
影响因子：
4
通讯作者：
T. Hiyama
中科院分区：
文献类型：
--
作者：
H. Yoshida;E. Shirakawa;Y. Nakao;Y. Honda;T. Hiyama
在钯-二亚胺络合物存在下，将炔双插入到炔基、烯基、烯丙基或芳基锡烷的 C-Sn 键中，得到具有独特顺式选择性的高度共轭的烯基锡烷。在丙炔酸乙酯与钯-1,2-双[(2,6-二异丙基苯基)亚氨基]苊络合物的二聚-碳锡烷基化中观察到完美的区域选择性，这使得甲锡烷基取代的粘康酸衍生物能够进行区域选择性和立体选择性合成。二聚-碳苯烷基化产物的π-缀合通过交叉偶联或同源偶联反应进一步延伸。提议将钯环戊二烯作为中间体物种。
Double insertion of alkynes into the C–Sn bond of an alkynyl-, alkenyl-, allyl- or arylstannane proceeded in the presence of a palladium–diimine complex to afford highly conjugated alkenylstannanes with exclusive syn selectivity. Perfect regioselectivities were observed in the dimerization–carbostannylation of ethyl propiolate with a palladium–1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene complex, which allowed regio- and stereoselective synthesis of stannyl-substituted muconic acid derivatives. The π-conjugation of the dimerization–carbostannylation products was further extended through a cross-coupling or homocoupling reaction. A palladacyclopentadiene is proposed as an intermediate species.