Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education and Laboratory of Organosilicon Material Technology of Zhejiang Province College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 311121, P. R. China.
State Key Laboratory for Oxo Synthesis and Selective Oxidation Suzhou Research Institute (SRI), Lanzhou Institute of Chemical Physics (LICP), University of the Chinese Academy of Sciences (UCAS), Lanzhou, 730000, P. R. China.
Chem Asian J. 2021 Jul 5;16(13):1730-1734. doi: 10.1002/asia.202100372. Epub 2021 May 18.
Organosilicon compounds are important reagents and synthetic intermediates that play a key role in the construction of new materials and complex products. Here we show a highly diastereoselective rhodium-catalyzed cycloisomerization of 1,6-dienes, in which the use of (EtO) SiH accelerates the intramolecular cyclization reaction to afford a novel spiro-fused succinimide and pyrazolone derivatives in moderate to excellent yields as a single diastereoisomer. The proposed mechanism involves an active Rh-H species from the hydrosilane that is the H-donor in this spiro-type cycloisomerization reaction.
有机硅化合物是重要的试剂和合成中间体，在新材料和复杂产品的构建中发挥着关键作用。在这里，我们展示了一种高非对映选择性的铑催化 1,6-二烯环异构化反应，其中（EtO）SiH 的使用加速了分子内环化反应，以中等至优异的收率得到了一种新型螺缩合琥珀酰亚胺和吡唑啉酮衍生物，作为单一非对映异构体。所提出的反应机制涉及来自硅烷的活泼 Rh-H 物种，它是这种螺环异构化反应中的 H 供体。
