Pyrrolidine-derived functionalizedchiralionicliquids (FCILs) have been found to catalyzeasymmetric S N 1 α-alkylations of ketones and aldehydes with up to 99 % yield, >99:1 dr and 87 % ee. The FCIL catalysts enable S N 1 α-alkylations of cyclicketones, particularly of 3- and 4-substituted cyclohexanones with excellent diastereoselectivity and good enantioselectivity, featuring unprecedented desymmetrization
已发现吡咯烷衍生的官能化手性离子液体 (FCIL) 可催化酮和醛的不对称 SN 1 α-烷基化反应,产率高达 99%,>99:1 dr 和 87% ee。FCIL 催化剂使环酮,特别是 3-和 4-取代环己酮的 SN 1 α-烷基化具有优异的非对映选择性和良好的对映选择性,为这些类型的不对称反应提供了前所未有的去对称化和动力学拆分过程。介绍了这项研究的全部细节以及提议的烯胺过渡态。
Asymmetric S<sub>N</sub>1 α-Alkylation of Cyclic Ketones Catalyzed by Functionalized Chiral Ionic Liquid (FCIL) Organocatalysts
Ionicliquid works better: The first intermolecular asymmetric α‐alkylation of cyclicketones was realized by using functionalizedchiralionicliquids as catalysts. The reaction proceeded with good to excellent yields and high ee. Highly stereoselective desymmetrization of 4‐substituted cyclohexanones with >99:1 d.r. and up to 87 % ee were achieved by using this protocol.