Copper(II)-mediated σ-metathesis with prochiral dihydrosilanes has been successfully leveraged to efficiently synthesize Si-chiral silanols as well as many other related Si-chiral skeletons. The reaction hinges on the continuous generation of catalytically active copper(II) species via single-electron transfer oxidation of copper(I) by alkyl halides and the efficient stereocontrol with multidentate
铜 (II) 介导的σ复分解与前手性二氢硅烷已成功用于有效合成 Si-手性硅烷醇以及许多其他相关的 Si-手性骨架。该反应取决于通过卤代烷对铜 (I) 进行单电子转移氧化连续生成具有催化活性的铜 (II),以及使用多齿阴离子 N,N,P-配体进行有效的立体控制。
Asymmetric aryl polyhedral oligomeric silsesquioxanes (ArPOSS) with enhanced solubility
作者:Brian M. Moore、Sean M. Ramirez、Gregory R. Yandek、Timothy S. Haddad、Joseph M. Mabry
DOI:10.1016/j.jorganchem.2011.03.035
日期:2011.7
Four new asymmetric Polyhedral Oligomeric SilSesquioxanes (POSS) with the formula (Aryl)Phenyl(7)-Si(8)O(12), where Aryl = 1-naphthyl, 2-naphthyl, 9-phenanthrenyl, and 1-pyrenyl, have been synthesized in reasonable yield and high purity. These compounds were characterized with (1)H, (13)C, (29)Si NMR and elemental combustion analysis. These compounds possess polycyclic aromatic functionality, which disrupts symmetry to improve solubility in organic solvents and aromatic polymers, without significant impact on thermal stability. Published by Elsevier B. V.