Amine attack on coordinated alkenes: An interconversion from anti-Markovnikoff to Markovnikoff products

被引:36
作者
Pryadun, R [1 ]
Sukumaran, D [1 ]
Bogadi, R [1 ]
Atwood, JD [1 ]
机构
[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA
关键词
D O I
10.1021/ja0469939
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A sequence of alkene complexes of platinum, PtCl2(PPh3)(alkene) (alkene = ethylene, propene, 1-butene, cis-2-butene, 1-hexene, 1-octene, and 1-decene), has been prepared. These complexes are characterized by NMR spectroscopy, including assignment of each proton, and X-ray crystal structures of the 1-propene and 1-hexene complexes. Each complex was reacted with diethylamine. For the 1-hexene, 1-octene, and 1-decene complexes, the amine displaces the alkene. For the smaller alkenes, the diethylamine nucleophilically attacks the coordinated alkene. For propene and 1-butene, the low-temperature addition leads to the anti-Markovnikoff nucleophilic attack, which slowly converts at room temperature to the Markovnikoff product. The transformation from anti-Markovnikoff to Markovnikoff addition occurs without diethylamine dissociation.
引用
收藏
页码:12414 / 12420
页数:7
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