Department of Chemistry , Zhejiang University , Hangzhou 310027 , China.
Department of Applied Chemistry , Zhejiang Gongshang University , Hangzhou 310018 , China.
Org Lett. 2018 Oct 19;20(20):6544-6549. doi: 10.1021/acs.orglett.8b02868. Epub 2018 Oct 8.
The first iron-catalyzed enantioselective Si-H bond insertion reaction of α-diazoesters was developed. A new chiral spiro-bisoxazoline ligand has proven to be an optimal ligand for the asymmetric reaction to give versatile chiral α-silyl esters in good yields with high enantioselectivities. The mechanism and detailed stereochemical models for enantioselective induction were elucidated by DFT calculations, suggesting that the reaction proceeds via a concerted quintet transition state.
发展了首例铁催化的α-重氮酯的对映选择性 Si-H 键插入反应。一种新型的手性螺双恶唑啉配体已被证明是该不对称反应的最佳配体，以高收率和高对映选择性得到多种手性α-硅基酯。通过 DFT 计算阐明了对映选择性诱导的反应机理和详细的立体化学模型，表明该反应通过协同五重态过渡态进行。
