Chemo- And regioselective intramolecular hydrosilylative carbocyclization of allenynes
Chemo- And regioselective intramolecular hydrosilylative carbocyclization of allenynes
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DOI：
10.1021/om049677b
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发表时间：
2004-07
期刊：
影响因子：
2.8
通讯作者：
T. Shibata;S. Kadowaki;K. Takagi
中科院分区：
文献类型：
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作者：
T. Shibata;S. Kadowaki;K. Takagi
在一氧化碳气氛下，各种烯丙炔和三烷氧基硅烷的硅氢化碳环化反应顺利进行，得到硅氢化环化产物。烯丙烯和炔的分子内偶联是化学和区域选择性的：硅烷化反应排他地进行到烯丙烯的内部烯烃部分，随后的碳金属化反应生成了环1，4-二烯。烷氧基硅烷的使用和烯丙烯末端取代基的使用对选择性起着关键作用。
Rhodium complex catalyzed hydrosilylative carbocyclization of various allenynes and trialkoxysilanes proceeded smoothly under an atmosphere of carbon monoxide to give hydrosilylated cyclic products. The intramolecular coupling of allene and alkyne is chemo- and regioselective: silylrhodation to an internal olefinic moiety of the allene proceeded exclusively, and subsequent carbometalation to the alkyne provided cyclic 1,4-dienes. The use of alkoxysilane and the substituents on the allene terminus play pivotal roles in the selectivity.