Tungsten(0)- and Rhenium(I)-Catalyzed Tandem Cyclization of Acetylenic Dienol Silyl Ethers Based on Geminal Carbo-Functionalization of Alkynes
Tungsten(0)- and Rhenium(I)-Catalyzed Tandem Cyclization of Acetylenic Dienol Silyl Ethers Based on Geminal Carbo-Functionalization of Alkynes
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DOI：
10.1002/chem.201003019
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发表时间：
2011-04-01
影响因子：
4.3
通讯作者：
Iwasawa, Nobuharu
中科院分区：
文献类型：
--
作者：
Kusama, Hiroyuki;Karibe, Yusuke;Iwasawa, Nobuharu
本文报道了基于炔烃的双碳官能化概念，钨(0)和Re(I)催化的二烯醇乙酰硅醚的反应。在光照条件下，3-硅氧基-1，3-二烯-7-YNE与催化量的[W(CO)(6)]或[RECl(CO)(5)]反应，以较好的产率合成了有用的双环[3.3.0]辛烷衍生物。Re(I)络合物具有极高的催化活性。该反应已扩展到其系链中含有氮原子的底物。在这种情况下，得到了两种合成上有用的杂环化合物-2-氮杂双环[3.3.0]辛烷衍生物9和带烯丙基取代基的单环二氢吡咯10，并且通过使用氮取代基和Re(I)催化剂类型的适当组合，可以选择性地制备这两种产物。2氮杂双环[3.3.0]辛烷衍生物9是通过在[RECl(CO)(4)(PPh3)]存在下对N-NS衍生物进行处理而选择性地得到的，而二氢吡咯衍生物10是通过用[RECl(CO)(5)]/AgSbF6处理N-MBS衍生物而得到的。最后，我们将这种双碳官能化应用于含有N-ts基团的一碳伸长的底物。在金(I)或Re(I)催化剂存在下，选择性的5-外环化反应得以实现，而在[W(CO)(6)]的存在下，6-内环化反应被观察到。
Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)(6)] or [ReCl(CO)(5)] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO)(4)(PPh3)], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)(5)]/AgSbF6. Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO)(6)].