Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides

An efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant and DMF as assisting liquid in the presence of anhydrous calcium chloride. Scope and limit...

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Main Authors: Xuanxuan Zhang, Yingying Hong, Gang Zou
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/30/5/1060
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author Xuanxuan Zhang
Yingying Hong
Gang Zou
author_facet Xuanxuan Zhang
Yingying Hong
Gang Zou
author_sort Xuanxuan Zhang
collection DOAJ
description An efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant and DMF as assisting liquid in the presence of anhydrous calcium chloride. Scope and limitations of the protocol to access diarylmethanes have been demonstrated with more than 20 examples, showing acceptable tolerance to functional group and steric hindrance. Although electron-withdrawing substituents on benzotriazinone or benzyl counterparts decrease the yields significantly, a series of N-alkyl-2-benzylbenzamides, diarylmethanes bearing an ortho-carbamoyl aryl group, could be obtained in modest to good yields.
format Article
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issn 1420-3049
language English
publishDate 2025-02-01
publisher MDPI AG
record_format Article
series Molecules
spelling doaj-art-b62bcf7902d8401bb4efdb21ae2e13792025-08-20T02:52:45ZengMDPI AGMolecules1420-30492025-02-01305106010.3390/molecules30051060Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl ChloridesXuanxuan Zhang0Yingying Hong1Gang Zou2School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Rd, Shanghai 200237, ChinaSchool of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Rd, Shanghai 200237, ChinaSchool of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Rd, Shanghai 200237, ChinaAn efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant and DMF as assisting liquid in the presence of anhydrous calcium chloride. Scope and limitations of the protocol to access diarylmethanes have been demonstrated with more than 20 examples, showing acceptable tolerance to functional group and steric hindrance. Although electron-withdrawing substituents on benzotriazinone or benzyl counterparts decrease the yields significantly, a series of N-alkyl-2-benzylbenzamides, diarylmethanes bearing an ortho-carbamoyl aryl group, could be obtained in modest to good yields.https://www.mdpi.com/1420-3049/30/5/1060diarylmethanebenzotriazinonecross-electrophile couplingnickel catalysisbenzylation
spellingShingle Xuanxuan Zhang
Yingying Hong
Gang Zou
Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
Molecules
diarylmethane
benzotriazinone
cross-electrophile coupling
nickel catalysis
benzylation
title Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
title_full Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
title_fullStr Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
title_full_unstemmed Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
title_short Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides
title_sort liquid assisted grinding enables efficient ni catalyzed mn mediated denitrogenative cross electrophile coupling of benzotriazinones with benzyl chlorides
topic diarylmethane
benzotriazinone
cross-electrophile coupling
nickel catalysis
benzylation
url https://www.mdpi.com/1420-3049/30/5/1060
work_keys_str_mv AT xuanxuanzhang liquidassistedgrindingenablesefficientnicatalyzedmnmediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithbenzylchlorides
AT yingyinghong liquidassistedgrindingenablesefficientnicatalyzedmnmediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithbenzylchlorides
AT gangzou liquidassistedgrindingenablesefficientnicatalyzedmnmediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithbenzylchlorides