Zhao Jia-Hui, Zheng Long, Zou Jian-Ye, Zhang Sheng-Ye, Shen Hua-Chen, Wu Yichen, Wang Peng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, 345 Lingling Road, Shanghai, 200032, China.
School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China.
Angew Chem Int Ed Engl. 2024 May 13;63(20):e202402612. doi: 10.1002/anie.202402612. Epub 2024 Mar 18.
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.
首次实现了在市售L-焦谷氨酸的协助下，通过钯催化的分子间C-H烯基化反应构建硅手性硅醇。以肟醚为导向基团，可以很容易地制备具有优异对映选择性的硅手性硅醇衍生物，底物范围广，官能团耐受性好。此外，不对称底物的平行动力学拆分进一步突出了该方法的通用性。机理研究表明，L-焦谷氨酸可以稳定钯催化剂并提供优异的手性诱导。初步的计算研究揭示了C-H键活化步骤中对映选择性的来源。
