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Beilstein journal of organic chemistry
2018;14 2250-2258.

Novel photochemical reactions of carbocyclic diazodiketones without elimination of nitrogen - a suitable way to N-hydrazonation of C-H-bonds.

Liudmila L Rodina, Xenia V Azarova, Jury J Medvedev, Dmitrij V Semenok, Valerij A Nikolaev
Author Information
  1. Liudmila L Rodina: Department of Organic Chemistry, St-Petersburg State University, 26 University pr., 198504, Saint-Petersburg, Russia. ORCID
  2. Xenia V Azarova: Department of Organic Chemistry, St-Petersburg State University, 26 University pr., 198504, Saint-Petersburg, Russia. ORCID
  3. Jury J Medvedev: Department of Organic Chemistry, St-Petersburg State University, 26 University pr., 198504, Saint-Petersburg, Russia. ORCID
  4. Dmitrij V Semenok: Skolkovo Institute of Science and Technology, 143026, Moscow, Skolkovo Innovation Center, 3 Nobel st., Russia.
  5. Valerij A Nikolaev: Department of Organic Chemistry, St-Petersburg State University, 26 University pr., 198504, Saint-Petersburg, Russia. ORCID
PMID: 30202479 DOI: 10.3762/bjoc.14.200

Abstract

The sensitized photoexcitation of 2-diazocyclopentane-1,3-diones in the presence of THF leads to the insertion of the terminal N-atom of the diazo group into the α-С-Н bond of THF, producing the associated -alkylhydrazones in yields of up to 63-71%. Further irradiation of hydrazones derived from furan-fused tricyclic diazocyclopentanediones culminates in the cycloelimination of furans to yield 2--(alkyl)hydrazone of cyclopentene-1,2,3-trione. By contrast, the direct photolysis of carbocyclic diazodiketones gives only Wolff rearrangement products with up to 90-97% yield.

Keywords

C–H insertion Wolff rearrangement diazo compounds excited state photochemistry

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Journal Article

Word Cloud

Created with Highcharts 10.0.0THFinsertiondiazoyieldcarbocyclicdiazodiketonesWolffrearrangementsensitizedphotoexcitation2-diazocyclopentane-13-dionespresenceleadsterminalN-atomgroupα-С-Нbondproducingassociated-alkylhydrazonesyields63-71%irradiationhydrazonesderivedfuran-fusedtricyclicdiazocyclopentanedionesculminatescycloeliminationfurans2--alkylhydrazonecyclopentene-123-trionecontrastdirectphotolysisgivesproducts90-97%Novelphotochemicalreactionswithouteliminationnitrogen-suitablewayN-hydrazonationC-H-bondsC–Hcompoundsexcitedstatephotochemistry

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