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A novel photocatalytic hydrazonyl radical-mediated radical cyclization/allylation cascade reaction of β,γ-unsaturated hydrazones is developed using allyl sulfones and Morita-Baylis-Hillman adduct as allyl sources, which provides an efficient and practical access to various diversely functionalized dihydropyrazoles and tetrahydropyridazines. The reaction is enabled by controllable generation of hydrazonyl radicals via an oxidative deprotonation electron transfer strategy and selective trapping of the resultant C-centered radicals under visible light irradiation.
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http://dx.doi.org/10.1021/acs.orglett.7b01609 | DOI Listing |
Angew Chem Int Ed Engl
April 2024
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
As a type of elementary organic compounds containing N-N single bond, hydrazone involved chemical conversions are extremely extensive, but they are mainly limited to N-retention and N-removal modes. We report herein an unprecedented protocol for the realization of division utilization of the N-moiety of hydrazone by a radical facilitated N-N bond deconstruction strategy. This new conversion mode enables the successful combination of alkene carboamination and Hofmann-Löffler-Freytag reaction by the reaction of N-homoallyl mesitylenesulfonyl hydrazones with ethyl difluoroiodoacetate under photocatalytic redox neutral conditions.
View Article and Find Full Text PDFJ Org Chem
February 2021
Department of Chemistry, University of Torino, Via Pietro Giuria, 7-10125 Torino, Italy.
Tetrahydropyridazines are of particular interest for their versatility as intermediates in organic synthesis and display pharmacological activity in several domains. Here, we describe the photocatalytic synthesis of different tetrahydropyridazines starting from γ,δ-unsaturated -arylsulfonylhydrazones. Simple structural changes of substrates result into three different pathways beginning from a common -hydrazonyl radical, which evolves through a domino carboamination/dearomatization, a HAT process, or a photoinduced radical Smiles rearrangement to afford diverse tetrahydropyridazines.
View Article and Find Full Text PDFOrg Lett
July 2017
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, China.
A novel photocatalytic hydrazonyl radical-mediated radical cyclization/allylation cascade reaction of β,γ-unsaturated hydrazones is developed using allyl sulfones and Morita-Baylis-Hillman adduct as allyl sources, which provides an efficient and practical access to various diversely functionalized dihydropyrazoles and tetrahydropyridazines. The reaction is enabled by controllable generation of hydrazonyl radicals via an oxidative deprotonation electron transfer strategy and selective trapping of the resultant C-centered radicals under visible light irradiation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2014
A visible-light photocatalytic generation of N-centered hydrazonyl radicals has been accomplished for the first time. This approach allows efficient intramolecular addition of hydrazonyl radical to terminal alkenes, thus providing hydroamination and oxyamination products in good yields. Importantly, the protocol involves deprotonation of an N-H bond and photocatalytic oxidation to an N-centered radical, thus obviating the need to prepare photolabile amine precursors or the stoichiometric use of oxidizing reagents.
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