Sequential silylcarbocyclization/silicon-based cross-coupling reactions
Sequential silylcarbocyclization/silicon-based cross-coupling reactions
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DOI：
10.1021/ja067854p
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发表时间：
2007-03-28
影响因子：
15
通讯作者：
Liu, Jack Hung-Chang
中科院分区：
文献类型：
--
作者：
Denmark, Scott E.;Liu, Jack Hung-Chang
以烯炔为原料，在铑催化下进行硅烷基碳环化反应，再与钯催化的硅基交叉偶联反应相结合，合成了高取代环戊烷。在铑催化剂存在下，1，6-烯炔与苄基二甲基硅烷反应，得到带有（Z）-亚烷基苄基硅基的五元环。各种取代模式和杂原子取代基是相容的。还实现了不饱和酯参与的硅烷基碳环化。所得亚烷基硅烷使用四正丁基氟化铵进行钯催化的交叉偶联。这种交叉偶联反应显示出广泛的底物范围。各种各样的取代模式，电子性质，和杂原子是兼容的。所有的交叉偶联反应在非常温和的条件下以高产率进行，并且完全保留了双键构型，得到密集官能化的3-（Z）-亚苄基环戊烷和杂环。
A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed for the synthesis of highly substituted cyclopentanes. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. The silylcarbocyclization in which an unsaturated ester participated was also achieved. The resulting alkylidenylsilanes underwent palladium-catalyzed cross-coupling using tetra-n-butylammonium fluoride. This cross-coupling reaction displayed a broad substrate scope. A wide variety of substitution patterns, electronic properties, and heteroatoms were compatible. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and heterocycles.