The Emergence of Anion−π Catalysis

作者：Yingjie Zhao, Yoann Cotelle, Le Liu, Javier López‐Andarias, Anna-Bea Bornhof, Masaaki Akamatsu, Naomi Sakai, Stefan Matile · 发表于：Accounts of Chemical Research · 年份：2018 · DOI：10.1021/acs.accounts.8b00223 · 被引用次数：242 · 研究领域：Lipid Membrane Structure and Behavior、Electrochemical Analysis and Applications、Molecular Sensors and Ion Detection

Conspectus The objective of this Account is to summarize the first five years of anion−π catalysis. The general idea of anion−π catalysis is to stabilize anionic transition states on aromatic surfaces. This is complementary to the stabilization of cationic transition states on aromatic surfaces, a mode of action that occurs in nature and is increasingly used in chemistry. Anion−π catalysis, however, rarely occurs in nature and has been unexplored in chemistry. Probably because the attraction of anions to π surfaces as such is counterintuitive, anion−π interactions in general are much younger than cation−π interactions and remain under-recognized until today. Anion−π catalysis has emerged from early findings that anion−π interactions can mediate the transport of anions across lipid bilayer membranes. With this evidence for stabilization in the ground state secured, there was no reason to believe that anion−π interactions could not also stabilize anionic transition states. As an attractive reaction to develop anion−π catalysis, the addition of malonic acid half thioesters to enolate acceptors was selected. This choice was also made because without enzymes decarboxylation is preferred and anion−π interactions promised to catalyze selectively the disfavored but relevant enolate addition. Concerning anion−π catalysts, we started with naphthalene diimides (NDIs) because their intrinsic quadrupole moment is highly positive. The NDI scaffold was used to address questions such as the ...