Mild Friedel-Crafts Reactions inside a Hexameric Resorcinarene Capsule: C-Cl Bond Activation through Hydrogen Bonding to Bridging Water Molecules

被引：77

作者：

La Manna, Pellegrino ^{[1
]}

Talotta, Carmen ^{[1
]}

Floresta, Giuseppe ^{[2
,3
]}

De Rosa, Margherita ^{[1
]}

Soriente, Annunziata ^{[1
]}

Rescifina, Antonio ^{[3
]}

Gaeta, Carmine ^{[1
]}

Neri, Placido ^{[1
]}

机构：

[1] Univ Salerno, Dipartimento Chim & Biol A Zambelli, Via Giovanni Paolo II 132, I-84084 Fisciano, Salerno, Italy

[2] Univ Catania, Dipartimento Sci Chim, Viale A Doria 6, I-95125 Catania, Italy

[3] Univ Catania, Dipartimento Sci Farmaco, Viale Andrea Doria 6, I-95125 Catania, Italy

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 19期

关键词：

Friedel-Crafts reaction; hydrogen bonding; resorcinarenes; self-assembled capsules; supramolecular catalysis; SELF-ASSEMBLED CAVITY; IMINIUM CATALYSIS; SELECTIVITY; EFFICIENT; REGIOSELECTIVITY; NUCLEOPHILICITY; ENCAPSULATION; ALKYLATIONS; REACTIVITY; PYRROLES;

D O I：

10.1002/anie.201801642

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel catalytic feature of a hexameric resorcinarene capsule is highlighted. The self-assembled cage was exploited to promote the Friedel-Crafts benzylation of several arenes and heteroarenes with benzyl chloride under mild conditions. Calculations showed that there are catalytically relevant hydrogen-bonding interactions between the bridging water molecules of the capsule and benzyl chloride, which is fundamental for the activation of the C-Cl bond. The capsule controls the reaction outcome. Inside the inner cavity of the capsule, N-methylpyrrole is preferentially benzylated in the unusual -position while mesitylene reacts faster than 1,3-dimethoxybenzene despite the greater -nucleophilicity of the latter compound.

引用

页码：5423 / 5428

页数：6

共 60 条

[1] Spontaneous formation of hexameric resorcinarene capsule in chloroform solution as detected by diffusion NMR [J].