- 用双齿亲核试剂取代苝酰亚胺：以芳氧基阴离子为例。

-Substitution of Perylene Bisimides with Bidentate Nucleophiles: The Case of Aryloxide Anions.

作者信息

Rivas Carlos J, Mena Leandro D, Baumgartner María T, Jimenez Liliana B

机构信息

Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Haya de la Torre y Medina Allende, Ciudad Universitaria. Córdoba, X5000HUA, Argentina.

INFIQC, Instituto de Investigaciones en Fisicoquímica de Córdoba (CONICET-UNC), Haya de la Torre s/n, Ciudad Universitaria. Córdoba, X5000HUA, Argentina.

出版信息

J Org Chem. 2024 Feb 16;89(4):2764-2770. doi: 10.1021/acs.joc.3c02002. Epub 2024 Jan 25.

DOI:10.1021/acs.joc.3c02002

PMID:38271990

Abstract

In this study, we delve into the regioselectivity of nucleophilic reactions involving brominated perylene bisimides (PBIs) and various bidentate aryloxide anions, previously associated with an S1 mechanism. We present herein a new perspective, suggesting that a single-electron-transfer aromatic nucleophilic substitution (SeT-SAr) mechanism is a more plausible scenario. Our study reveals the favorable impact of photostimulation on reaction yields, making our method a convenient approach for accessing arylated PBIs.

摘要

在本研究中，我们深入探究了涉及溴代苝双酰亚胺（PBIs）和各种双齿芳氧基阴离子的亲核反应的区域选择性，这些反应之前被认为与S1机理相关。我们在此提出一种新观点，认为单电子转移芳香亲核取代（SeT-SAr）机理是更合理的情况。我们的研究揭示了光刺激对反应产率的有利影响，使我们的方法成为获得芳基化PBIs的便捷途径。