可见光催化诱导的Smiles重排研究进展

doi:10.6023/A19050179

摘要/Abstract

Smiles重排反应是有机合成中被广泛使用的人名反应之一, 是芳基化合物构建策略的一种独特方法. Smiles重排经历了近一个世纪的发展, 从传统的离子型Smiles反应、Truce-Smiles反应等, 发展到后期的自由基型Smiles重排, 这些进展极大地丰富了该反应在合成化学、材料化学等领域的应用. 近年来, 光催化氧化还原反应获得了广泛关注, 这一新颖催化模式高效利用光能, 能在温和的条件下产生自由基中间体, 实现了很多选择性反应. 过去的五年中, 化学家逐渐将这一催化模式应用到了Smiles重排反应中, 发展了一系列新颖、实用的合成方法. 本文对这些进展进行综述, 主要依据促进重排反应的自由基种类和成键类型进行分类.

关键词: 可见光催化, Smiles重排, 自由基重排

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.

Key words: visible-light photocatalysis, Smiles rearrangement, radical rearrangement

引用此文

陈奕霖, 常亮, 左智伟. 可见光催化诱导的Smiles重排研究进展[J]. 化学学报, 2019, 77(9): 794-802.

Chen, Yilin, Chang, Liang, Zuo, Zhiwei. Visible Light Photoredox-Induced Smiles Rearrangement[J]. Acta Chimica Sinica, 2019, 77(9): 794-802.

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图/表 20

图1. 经典Smiles重排与光催化Smiles重排反应

Figure 1. Generalized Smiles rearrangement and photoredox Smiles rearrangement

图2. 可见光催化的杂环芳基磺酸酯的Smiles重排反应

Figure 2. The visible light mediated Smiles rearrangement of aromatic sulfonates

图3. 可见光促进的杂环芳基磺酸酯的Smiles重排反应机理

Figure 3. Proposed mechanism for the visible light mediated Smiles rearrangement of aromatic sulfonates

图4. 可见光催化的杂环芳胺的Smiles重排反应

Figure 4. The visible light mediated Smiles rearrangement of aromatic amines

图5. 可见光催化的杂环芳胺的Smiles重排反应机理

Figure 5. Proposed mechanism for the visible-light mediated Smiles rearrangement of aromatic amines

图6. 通过可见光催化还原羰基官能团引发Smiles重排反应

Figure 6. Smiles rearrangement mediated by reduction of carbonyl through visible-light photoredox catalysis

图7. 通过可见光催化不饱和键官能团化诱导Smiles重排

Figure 7. Smiles rearrangement mediated by functionalization of unsaturated C—C bond through visible-light photoredox catalysis

图8. 可见光催化Smiles重排介导的烯烃胺芳基化反应

Figure 8. Alkene aminoarylation through visible-light photocatalytic Smiles rearrangement

图9. 可见光催化Smiles重排介导的烯烃胺芳基化反应机理

Figure 9. Proposed mechanism for alkene aminoarylation through visible-light photocatalytic Smiles rearrangement

图10. 可见光催化Smiles重排介导的烯烃二氟甲基化反应

Figure 10. Alkene difluoromethylation through visible-light photocatalytic Smiles rearrangement

图11. 可见光催化Smiles重排介导的烯烃二氟甲基化反应机理

Figure 11. Proposed mechanism for alkene difluoromethylation through visible-light photocatalytic Smiles rearrangement

图12. 烯基醇类底物作为可见光催化Smiles重排前体实现烯烃的双官能团化

Figure 12. Bifunctionalization of alkenes through visible-light photocatalytic Smiles rearrangement of vinyl alcohol

图13. 光催化Smiles重排介导的叔醇δ远端C(sp3)—H键活化

Figure 13. Remote C(sp3)—H bonds activation of tertiary alcohol through photoredox catalyzed Smiles rearrangement

图14. 基于可见光催化Smiles重排的脂肪胺氮γ位C—C键活化官能团化

Figure 14. γ-Functionalizations of amines through visible-light photocatalytic Smiles rearrangement

图15. 脂肪胺氮γ位C—C键活化官能团化反应机理

Figure 15. Proposed mechanism for γ-functionalization of amines

图16. 由可见光催化Smiles重排介导的中环内酰胺合成

Figure 16. Synthesis of medium-sized lactams mediated by visible-light photocatalytic Smiles rearrangement

图17. 中环内酰胺合成反应机理

Figure 17. Proposed mechanism for synthesis of medium-sized lactams

图18. 可见光催化Smiles重排介导的芳基醚转化成酯的反应

Figure 18. Transformation from aryl ethers to esters through visible- light photocatalytic Smiles rearrangement

图19. 可见光催化Smiles重排介导的芳基醚转化成酯的反应机理

Figure 19. Proposed mechanism for transformation from aryl ethers to esters through visible-light photocatalytic Smiles rearrangement

图20. 可见光催化酰基自由基Smiles重排构建羟基二苯甲酮

Figure 20. Acyl radical Smiles rearrangement to construct hydroxybenzophenones through photoredox catalysis

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