Dedicated to Professor Yashwant D. Vankar on the occasion of his 70^th birthday

Abstract

Cyclic ketones, anhydrides, lactams and lactones are a particular class of molecules that are often used in synthesis, wherein their electrophilic properties are leveraged to enable facile Friedel–Crafts ring openings through nucleophilic attack at the carbonyl sp² centre. The use of electron-rich alkoxybenzenes as nucleophiles has also become important since the discovery of the Friedel–Crafts reaction. As a result, various isomeric alkoxybenzenes are used for preparing starting materials in target-oriented syntheses. This review covers the instances of different alkoxybenzenes that are used as nucleophiles in ring-opening acylations with carbonyl-containing cyclic electrophiles, for the construction of important building blocks for multistep transformations. This review summarizes the ring-opening functionalization of three- to seven-membered molecular rings with alkoxybenzenes in a Friedel–Crafts fashion. Sometimes the rings need subtle or considerable activation by the help of Lewis acid(s), followed by nucleophilic attack. This review is aimed to be a summary of the important acylations of electron-rich alkoxybenzenes by nucleophilic ring-opening of cyclic molecules. The works cited employ a wide range of conditions and differently substituted substrates for target-oriented syntheses.

1 Introduction and Scope

2 Arenes for Acylative Ring Opening

2.1 Three-Membered Rings: Ring Opening of Oxirane-2,3-dione

2.2 Four-Membered Rings

2.2.1 Ring Opening of Cyclobutanones

2.2.2 Ring Opening of β-Lactams

2.2.3 Ring Opening of β-Lactone

2.3 Five-Membered Rings

2.3.1 Ring Opening of Phthalimides

2.3.2 Ring Opening of γ-Lactones

2.3.3 Ring Opening of Anhydrides

2.4 Six-Membered Rings

2.5 Seven-Membered Rings

3 Conclusion

Publication History

Received: 18 June 2020

Accepted after revision: 20 July 2020

Publication Date:
08 September 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

中文翻译：

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烷氧基苯的重要合成开环酰基

专用于亚什万特D. Vankar教授在他的70之际^个生日

抽象

环酮，酸酐，内酰胺和内酯是合成中经常使用的一类特殊分子，其中亲电子特性被利用，以通过对羰基sp ^2的亲核攻击来实现容易的Friedel-Crafts开环中央。自从发现Friedel-Crafts反应以来，使用富电子的烷氧基苯作为亲核试剂也变得很重要。结果，各种异构体烷氧基苯被用于制备目标定向合成中的起始原料。这篇综述涵盖了不同烷氧基苯的实例，这些烷氧基苯在与含羰基的环状亲电试剂的开环酰化反应中用作亲核试剂，用于构建多步转化的重要构件。这篇综述总结了Friedel-Crafts方法用烷氧基苯对三元至七元分子环的开环官能化。有时，在路易斯酸的帮助下，需要对环进行微妙或相当大的激活，然后进行亲核攻击。这篇综述的目的是通过环状分子的亲核开环来概括富电子的烷氧基苯的重要酰化反应。所引用的著作采用了广泛的条件和针对目标合成的不同取代的底物。

1引言与范围

2种用于开环酰基的芳烃

2.1三元环：Oxirane-2,3-dione的开环

2.2四元环

2.2.1环丁酮的开环

2.2.2β-内酰胺的开环

2.2.3β-内酯的开环

2.3五圆环

2.3.1邻苯二甲酰亚胺的开环

2.3.2γ-内酯的开环

2.3.3酸酐的开环

2.4六元环

2.5七圆环

3结论

出版历史

收到：2020年6月18日

修订后接受：2020年7月20日

发布日期：
2020年9月8日（在线）

©2020年。Thieme。版权所有

Georg Thieme Verlag
KGRüdigerstraße14，70469斯图加特，德国