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Visible Light Photoredox-Induced Smiles Rearrangement
Acta Chimica Sinica ( IF 2.5 ) Pub Date : 2019-01-01 , DOI: 10.6023/a19050179 Yilin Chen , Liang Chang , Zhiwei Zuo
Acta Chimica Sinica ( IF 2.5 ) Pub Date : 2019-01-01 , DOI: 10.6023/a19050179 Yilin Chen , Liang Chang , Zhiwei Zuo
The intramolecular aromatic ring systems migration reactions, namely Smiles rearrangement is a powerful method for (hetero) aryl group functionalization. It can be employed as a complementary strategy to arene functionalization, and has found its broad applications in synthetic chemistry. After the initial documentation in 1894 this chemistry was intensively investigated by Smiles. In its classical pathway, the migration of aromatic ring system takes place ipso nucleophilic substitution. Accordingly, the migrating (hetero) aryl groups are highly electronic and steric-dependent. Moreover, as new reaction modes reported, advances have been made in the areas for arene C-C, C-N and C-O bond formation and radical triggered Smiles rearrangement has also enriched migrating units. Recently, there has been a rapid growth in the transformation induced by visible-light photocatalysis. Harnessing visible light as the energy source for chemical reactions usually serves as an environmentally benign alternative in comparison with classical radical pathway. Furthermore, photoredox-induced rearrangement represents a valuable and efficient approach for facilitating both the radical-based bond-cleaving and bond-forming events in a single step. It has become an effective tool for both synthesis and late stage modification of bio-active molecules. The last five years has witnessed many important advances in exploring photo-induced Smiles reactions, which make this classic reaction regained its attention. Significant progress has been made for expediting the generation of N-centered, C-centered and O-centered from a variety of precursors before single electron transfer rearrangement. This powerful synthetic platform for efficient promotes (hetero) aromatic group construction under mild reaction conditions, and has become a useful method for the synthesis and late stage functionalization of pharmaceutically interest products. In this perspective, we focus on visible light induced Smiles chemistry, which the major breakthroughs are classified based on migrating-induced radical species, and their synthetic applications are discussed briefly.
中文翻译:
可见光光氧化还原诱导的微笑重排
分子内芳环系统迁移反应,即 Smiles 重排是(杂)芳基官能化的有力方法。它可以用作芳烃功能化的补充策略,并在合成化学中得到了广泛的应用。在 1894 年首次记录之后,Smiles 对这种化学进行了深入研究。在其经典途径中,芳环系统的迁移发生在亲核取代上。因此,迁移的(杂)芳基是高度电子和空间依赖性的。此外,随着新反应模式的报道,芳烃 CC、CN 和 CO 键形成领域取得了进展,自由基引发的 Smiles 重排也丰富了迁移单元。最近,可见光光催化引起的转化迅速增长。与经典自由基途径相比,利用可见光作为化学反应的能源通常是一种环境友好的替代方案。此外,光氧化还原诱导的重排代表了一种有价值且有效的方法,可在单个步骤中促进基于自由基的键断裂和键形成事件。它已成为生物活性分子合成和后期修饰的有效工具。过去五年,在探索光诱导微笑反应方面取得了许多重要进展,使这一经典反应重新受到关注。在加快生成以 N 为中心的、在单电子转移重排之前,来自各种前体的 C 中心和 O 中心。这种强大的合成平台可在温和的反应条件下有效促进(杂)芳香基团的构建,并已成为合成和后期功能化药物相关产品的有用方法。从这个角度来看,我们专注于可见光诱导微笑化学,主要突破基于迁移诱导的自由基物种进行分类,并简要讨论它们的合成应用。
更新日期:2019-01-01
中文翻译:
可见光光氧化还原诱导的微笑重排
分子内芳环系统迁移反应,即 Smiles 重排是(杂)芳基官能化的有力方法。它可以用作芳烃功能化的补充策略,并在合成化学中得到了广泛的应用。在 1894 年首次记录之后,Smiles 对这种化学进行了深入研究。在其经典途径中,芳环系统的迁移发生在亲核取代上。因此,迁移的(杂)芳基是高度电子和空间依赖性的。此外,随着新反应模式的报道,芳烃 CC、CN 和 CO 键形成领域取得了进展,自由基引发的 Smiles 重排也丰富了迁移单元。最近,可见光光催化引起的转化迅速增长。与经典自由基途径相比,利用可见光作为化学反应的能源通常是一种环境友好的替代方案。此外,光氧化还原诱导的重排代表了一种有价值且有效的方法,可在单个步骤中促进基于自由基的键断裂和键形成事件。它已成为生物活性分子合成和后期修饰的有效工具。过去五年,在探索光诱导微笑反应方面取得了许多重要进展,使这一经典反应重新受到关注。在加快生成以 N 为中心的、在单电子转移重排之前,来自各种前体的 C 中心和 O 中心。这种强大的合成平台可在温和的反应条件下有效促进(杂)芳香基团的构建,并已成为合成和后期功能化药物相关产品的有用方法。从这个角度来看,我们专注于可见光诱导微笑化学,主要突破基于迁移诱导的自由基物种进行分类,并简要讨论它们的合成应用。