亲电硒催化重排反应的研究进展

doi:10.6023/cjoc202508009

摘要/Abstract

在硒作为催化中心参与的各类反应中, 亲电硒催化凭借其独特的亲碳性与氧化还原活性等优势, 已成为催化合成领域的重要工具, 并在过去十年间受到学术界的广泛关注. 该催化策略被应用于各类重排反应中, 可顺利构建各种有价值的化合物. 本综述简要概括了亲电硒催化在重排反应中的研究进展, 重点从亲核重排和[2,3] σ重排两个方面进行阐述, 着重剖析相关反应机理，以期为新型硒催化反应的设计提供参考.

关键词: 亲电硒催化, 亲核重排, [2,3] σ重排, 有机催化

Among the various reactions in which selenium serves as a catalytic center, electrophilic selenium catalysis has become an important synthetic tool in catalytic synthesis and has received increasing attention over the past decade, owing to its unique catalytic advantages such as carbon affinity and redox activity. This catalytic method has also been applied in various rearrangement reactions and can successfully construct a variety of valuable compounds. This review briefly summarizes the research progress of electrophilic selenium catalysis in rearrangement reactions, introducing both nucleophilic rearrangements and [2,3] sigmatropic rearrangements, with a focus on the description of reaction mechanisms, providing references for the design of new selenium-catalyzed reactions.

Key words: electrophilic selenium catalysis, nucleophilic rearrangement, [2,3] σ rearrangement, organocatalysis

引用此文

仇王朕, 赵晓丹. 亲电硒催化重排反应的研究进展[J]. 有机化学, 2026, 46(5): 2002-2009.

Wangzhen Qiu, Xiaodan Zhao. Research Progress in Electrophilic Selenium-Catalyzed Rearrangement Reactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 2002-2009.

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图/表 15

图式1. 过渡金属和亲电硒与π键的作用模式

Scheme 1. Interaction modes between transition metal/electro- philic selenium and π bonds

图式2. Wagner-Meerwein型重排反应机理

Scheme 2. Mechanism of Wagner-Merwein type reaction

图式3. 亲电硒催化下烯烃经碳正离子中间体发生重排反应的一般机理

Scheme 3. General mechanism of electrophilic selenium catalyzed rearrangement reactions of alkenes via cationic intermediates

图式4. 亲电硒催化烯烃分子内C—H胺化反应构建取代吲哚

Scheme 4. Construction of substituted indoles by electrophilic selenium catalyzed intramolecular C—H amination of alkenes

图式5. 亲电硒催化的烯烃偕二叠氮化反应

Scheme 5. 1,1-Diazidation of alkenes by electrophilic selenium catalysis TMPyF＋BF4－=1-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate

图式6. 亲电硒催化的烷基取代烯烃和三取代烯烃偕二叠氮化反应

Scheme 6. 1,1-Diazidation of alkyl-substituted and trisubstituted alkenes by electrophilic selenium catalysis

图式7. 分子内氧迁移反应的机理

Scheme 7. Mechanism of intramolecular O-migration reaction

图式8. 亲电硒催化烯丙基醇类底物氧迁移反应

Scheme 8. Electrophilic selenium-catalyzed oxygen migration reaction of allylic alcohol-type substrates

图式9. 亲电硒催化炔丙基膦酸酯通过氧迁移构建炔酮

Scheme 9. Electrophilic selenium-catalyzed construction of alkynyl ketones from propargyl phosphonates via O-migration

图式10. 经酯基迁移的亲电硒催化烯烃的双官能团化

Scheme 10. Electrophilic selenium-catalyzed difunctionalization of alkenes via ester group migration

图式11. 电化学氧化促进的亲电硒催化邻硝基苯炔分子内氧转移环化反应

Scheme 11. Electrophilic selenium-catalyzed intramolecular O- migration cyclization of o-nitrophenylalkynes promoted by electrochemical oxidation

图式12. 亲电硒催化的苯酚对位氨基化反应

Scheme 12. Electrophilic selenium-catalyzed p-amination of phenols NPhth=phthalimide

图式13. 亲电硒催化的苯酚对位氨基化反应的密度泛函理论计算研究

Scheme 13. DFT study on electrophilic selenium-catalyzed p- amination of phenol

图式14. 亲电硒催化的N-芳基异羟肟酸重排反应

Scheme 14. Electrophilic selenium-catalyzed rearrangement reaction of N-aryl Hydroxamic acids

图式15. 电化学氧化促进的亲电硒催化苯酚对位氨基化反应

Scheme 15. Electrophilic selenium-catalyzed p-amination of phenols promoted by electrochemical oxidation

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