Application of fluoride-catalyzed silane reductions of tin halides to the in situ preparation of vinylstannanes
Application of fluoride-catalyzed silane reductions of tin halides to the in situ preparation of vinylstannanes
复制标题
DOI：
10.1021/jo990491
复制
发表时间：
1999-08-06
影响因子：
3.6
通讯作者：
Terstiege, I
中科院分区：
文献类型：
--
作者：
Maleczka, RE;Terrell, LR;Terstiege, I
我们发现，无论是Bu3SnCl/PMHS/KF(AQ)，还是三丁基氟化锡、PMHS和催化量的四丁基氟化铵的组合，都可以作为三丁基锡氢化物的原位来源，用于自由基和钯催化的氢化锡化反应。这些方法对包括硅醚在内的各种官能团都是宽容的，而且在这些条件下，Me3SnCl也被还原，为Me3SnH的形成和反应提供了一种相对方便和安全的方式。我们还观察到，Bu3SnCl/硅氧烷/氟化物的组合比现有的将1-溴代炔转化为反式-1-(三丁基锡基)-1-烯烃的方案有了改进。具体地说，KF/PMHS方法允许1-溴炔在单个锅中生成并与亚化学计量比的锡反应。最后，替代的还原剂，如Red-Sil也适用于该方法。
We have found that either Bu3SnCl/PMHS/KF(aq), or the combination of tributyltin fluoride, PMHS, and catalytic quantities of tetrabutylammonium fluoride can serve as in situ sources of tributyltin hydride for both free radical and palladium-catalyzed hydrostannylation reactions. These methods are tolerant of a variety of functional groups, including silyl ethers, Furthermore, Me3SnCl is also reduced under these conditions, providing a relatively convenient and safe manner by which Me3SnH can be formed and reacted. We have also observed that the Bu3SnCl/siloxane/fluoride combination offers improvements over the existing protocols for transforming 1-bromoalkynes into trans-1-(tributylstannyl)-1-alkenes. Specifically, the KF/PMHS methodology allows the 1-bromoalkyne to be formed and reacted in a single pot and with substoichiometric amounts of tin. Finally, alternative reductants such as Red-Sil are also amenable to the method.