He Tao, Liu Li-Chuan, Guo Le, Li Bin, Zhang Qing-Wei, He Wei
School of Pharmaceutical Sciences and MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Tsinghua University, Beijing, 100084, P. R. China.
Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Angew Chem Int Ed Engl. 2018 Aug 20;57(34):10868-10872. doi: 10.1002/anie.201804223. Epub 2018 Jul 19.
Disilylation of alkynes could provide rapid entry to synthetically useful 1,2-bissilyl-alkenes, but is currently limited to activated disilanes reacting in an intramolecular fashion. Reported herein is an efficient rhodium(I)-catalyzed intermolecular disilylation of a wide array of alkynones with unactivated disilanes. Importantly, this reaction produces exclusively trans-disilylation products, selectivity that has been rarely reported. These disilylation products were transformed into interesting pentacyclic vinyl silane ethers, among other additional synthetic manipulations. Mechanistic studies uncovered that the unactivated disilanes underwent facile Si-Si activation and crossover under the reaction conditions.
炔烃的二硅基化反应可以快速得到具有合成价值的1,2-双硅基烯烃，但目前仅限于分子内反应的活性二硅烷。本文报道了一种高效的铑（I）催化的各种炔酮与未活化二硅烷的分子间二硅基化反应。重要的是，该反应仅生成反式二硅基化产物，这种选择性很少被报道。这些二硅基化产物经过其他一些合成操作后，转化为有趣的五环乙烯基硅醚。机理研究发现，未活化的二硅烷在反应条件下容易发生硅-硅活化和交叉反应。
