Research Progress in Electrophilic Selenium-Catalyzed Rearrangement Reactions

doi:10.6023/cjoc202508009

Abstract

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

Cite this article

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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Fig. & Tab. 15

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

Scheme 2. Mechanism of Wagner-Merwein type reaction

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

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

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

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

Scheme 7. Mechanism of intramolecular O-migration reaction

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

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

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

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

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

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

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

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

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