手性 1,2-二胺催化动力学拆分β-位无官能化伯醇的实验与计算综合研究：非共价相互作用的重要性。

Integrated Experimental and Computational Studies on the Organocatalytic Kinetic Resolution of β-Unfunctionalized Primary Alcohols Using a Chiral 1,2-Diamine: The Importance of Noncovalent Interactions.

机构信息

Department of Chemistry, Faculty of Science, Ibaraki University, 2-1-1 Bunkyo, Mito, Ibaraki 310-8512, Japan.

Institute of Quantum Beam Science, Ibaraki University, 2-1-1 Bunkyo, Mito, Ibaraki 310-8512, Japan.

出版信息

J Org Chem. 2022 Mar 18;87(6):4468-4475. doi: 10.1021/acs.joc.1c03033. Epub 2022 Feb 24.

DOI:10.1021/acs.joc.1c03033

PMID:35199522

Abstract

The enantioselective kinetic resolution of β-unfunctionalized primary alcohols with benzoyl chloride was carried out in the presence of a catalytic amount of a novel chiral 1,2-diamine derived from ()-proline. Several valuable chiral 2-substituted propan-1-ols were obtained with good enantioselectivities. Density functional theory calculations revealed that the noncovalent interaction, such as CH-π interaction, is crucial for the enantioselectivity of the resolution. This study was conducted through an interplay between experiment and computation.

摘要

在新型手性 1,2-二胺（来源于（）-脯氨酸）的催化量存在下，对β-无官能化伯醇与苯甲酰氯进行对映选择性动力学拆分。通过实验和计算的相互作用，获得了几种具有良好对映选择性的有价值的手性 2-取代丙-1-醇。密度泛函理论计算表明，非共价相互作用（如 CH-π 相互作用）对拆分的对映选择性至关重要。