Rhodium-Catalyzed Enantioselective Intramolecular CH Silylation for the Syntheses of Planar-Chiral Metallocene Siloles
作者:Qing-Wei Zhang、Kun An、Li-Chuan Liu、Yuan Yue、Wei He
DOI:10.1002/anie.201502548
日期:2015.6.1
Reported herein is the rhodium‐catalyzed enantioselective CH bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)‐TMS‐Segphos, the reactions took place under very mild conditions to afford metallocene‐fused siloles in good to excellent yields and with ee values of up to 97 %. During this study it was observed that the steric hindrance of chiral ligands
本文报道的是Fe和Ru茂金属中的环戊二烯环的铑催化的对映选择性CH键甲硅烷基化。因此,在(S)-TMS-Segphos的存在下,反应在非常温和的条件下进行,从而获得了茂金属熔融的硅酮,产率高至优异,ee 值高达97%。在这项研究中,观察到手性配体的空间位阻对反应的反应性和对映选择性有深远的影响,并且可能是完成常规具有挑战性的不对称CH甲硅烷基化的关键。