Rhodium(II)-catalyzed CH insertions with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda(3)-iodane
Rhodium(II)-catalyzed CH insertions with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda(3)-iodane
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DOI：
10.1002/hlca.19970800407
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发表时间：
1997-01-01
影响因子：
1.8
通讯作者：
Muller, P
中科院分区：
文献类型：
--
作者：
Nageli, I;Baud, C;Muller, P
[Rh-2(OAc)(4)]催化的{[（4-硝基苯基）磺基]亚胺}苯基-lambda(3)-碘烷（NsN = IPh）的分解导致CH键的正式插入，由苯基或乙烯基或o取代基激活。研究了该反应的范围和局限性。在最有利的情况下，产量可达84%。释放电子取代基提高了产率，位阻降低了产率。叠氮化与烯丙基插入在烯烃底物上竞争。插入反应继续进行，构型保持不变。使用手性Rh-II催化剂，观察到适度的不对称诱导。提出了一种由rh络合的亚硝基直接插入CH键的机制。
The [Rh-2(OAc)(4)]-catalyzed decomposition of {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda(3)-iodane (NsN = IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhanced by electron-releasing substituents and decreased by steric hindrance. Aziridination competed with allylic insertion with olefinic substrates. The insertion reaction proceeded with retention of configuration. With chiral Rh-II catalysts, a modest asymmetric induction was observed. A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.