W(CO)5(L)-catalyzed tandem intramolecular cyclopropanation/cope rearrangement for the stereoselective construction of bicyclo[5.3.0]decane framework.
W(CO)5(L)-catalyzed tandem intramolecular cyclopropanation/cope rearrangement for the stereoselective construction of bicyclo[5.3.0]decane framework.
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DOI：
10.1021/ja0671924
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发表时间：
2006-12
影响因子：
15
通讯作者：
H. Kusama;Yuji Onizawa;N. Iwasawa
中科院分区：
文献类型：
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作者：
H. Kusama;Yuji Onizawa;N. Iwasawa
利用亲电活化炔烃的双卡宾特性，在W(CO)5(L)催化下，实现了3-硅氧基-1,3,9-三-7-炔的分子内串联环丙化/Cope重排，用于立体选择性构建双环[5.3.0]十烷骨架。以W(CO)6催化量在光照射下处理3-硅氧基-1,3,9-三-7-炔，立体选择性地得到了收率较高的双环[5.3.0]癸烷。在该反应中，基于W(CO)5(L)催化的炔烃亲电活化，由3-硅氧基-1,3,9-三-7-炔分子内环丙烷化反应产生的二乙烯基环丙烷中间体发生了Cope重排，立体选择性地生成了合成有用的功能化双环[5.3.0]十烷衍生物。
Utilizing the biscarbene character of electrophilically activated alkynes, a novel tandem intramolecular cyclopropanation/Cope rearrangement of 3-siloxy-1,3,9-trien-7-ynes catalyzed by W(CO)5(L) for the stereoselective construction of bicyclo[5.3.0]decane framework is achieved. When 3-siloxy-1,3,9-trien-7-ynes were treated with a catalytic amount of W(CO)6 under photoirradiation, bicyclo[5.3.0]decanes were obtained in good yield stereoselectively. In this reaction, the Cope rearrangement of the divinylcyclopropane intermediates, generated by the intramolecular cyclopropanation of 3-siloxy-1,3,9-trien-7-ynes based on the W(CO)5(L)-catalyzed electrophilic activation of alkynes, occurs to give synthetically useful functionalized bicyclo[5.3.0]decane derivatives stereoselectively.