中国科学院上海有机化学研究所王鹏团队报道了钯催化对映选择性C–H烯基化构建硅立体烷醇。相关研究成果于2024年2月27日发表在《德国应用化学》。

研究人员首次实现了在市售L-焦谷氨酸的帮助下，通过Pd催化的分子间C–H烯基化构建硅立体硅醇。以肟醚为导向基团，可以制备具有良好对映选择性、底物范围广、官能团耐受性好的硅立体硅醇衍生物。

此外，不对称底物的平行动力学分辨率进一步突出了该方案的通用性。机理研究表明，L-焦谷氨酸可以稳定钯催化剂，并提供良好的手性诱导作用。初步的计算研究揭示了C–H键活化步骤中对映选择性的起源。

附：英文原文

Title: Construction of Si-Stereogenic Silanols by Palladium-Catalyzed Enantioselective C–H Alkenylation

Author: Jia-Hui Zhao, Long Zheng, Jian-Ye Zou, Sheng-Ye Zhang, Hua-Chen Shen, Yichen Wu, Peng Wang

Issue&Volume: 2024-02-27

Abstract: The construction of silicon-stereogenic silanols via Pd-catalyzed intermolecular C–H alkenylation with the assistance of a commercially available L-pyroglutamic acid has been realized for the first time. Employing oxime ether as the directing group, silicon-stereogenic silanol derivatives could be readily prepared with excellent enantioselectivities, featuring a broad substrate scope and good functional group tolerance. Moreover, parallel kinetic resolution with unsymmetric substrates further highlighted the generality of this protocol. Mechanistic studies indicate that L-pyroglutamic acid could stabilize the Pd catalyst and provide excellent chiral induction. Preliminary computational studies unveil the origin of the enantioselectivity in the C–H bond activation step.

DOI: 10.1002/anie.202402612

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202402612