Institute of Organic Chemistry, Faculty of Chemistry, Lodz University of Technology, Żeromskiego 116, 90-924 Łódź, Poland.
Org Lett. 2022 Jan 28;24(3):955-959. doi: 10.1021/acs.orglett.1c04328. Epub 2022 Jan 18.
In this paper, the application of differentiating catalysis in the [4 + 2]-cycloaddition between 2-alkyl-3-formylheteroarenes and α,β-unsaturated aldehydes is described. Within the developed approach, the same aminocatalyst is employed for the independent activation of both starting materials, differentiating their properties via LUMO-lowering and HOMO-rising principles. By the combination of dearomative dienamine activation with iminium ion chemistry high enantio- and diastereoselectivity of the doubly asymmetric process was accomplished. Selected transformations of products were also demonstrated.
本文描述了差异化催化在 2-烷基-3-甲酰基杂芳烃和α,β-不饱和醛的[4+2]-环加成反应中的应用。在开发的方法中，相同的氨基催化剂被用于独立激活两种起始原料，通过降低最低未占轨道（LUMO）和升高最高占据轨道（HOMO）的原则来区分它们的性质。通过去芳构化的二烯胺激活与亚胺离子化学的结合，实现了双重不对称过程的高对映选择性和非对映选择性。还展示了所选产物的转化。
