Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates
An efficient Ni-catalyzed, Mn-mediated denitrogenative cross-electrophile coupling of <i>N</i>-alkyl-1,2,3-benzotriazinones with alkyl tosylates and mesylates for access to <i>o</i>-alkyl secondary benzamides is reported. The method uses inexpensive non-anhydrous dimethyl ace...
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MDPI AG
2025-05-01
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| author | Yingying Hong Xuanxuan Zhang Gang Zou |
| author_facet | Yingying Hong Xuanxuan Zhang Gang Zou |
| author_sort | Yingying Hong |
| collection | DOAJ |
| description | An efficient Ni-catalyzed, Mn-mediated denitrogenative cross-electrophile coupling of <i>N</i>-alkyl-1,2,3-benzotriazinones with alkyl tosylates and mesylates for access to <i>o</i>-alkyl secondary benzamides is reported. The method uses inexpensive non-anhydrous dimethyl acetamide (DMA) in combination with tetrabutyl ammonium iodide (TBAI) as a co-catalyst to convert sulfonates into iodides in situ. Scope and limitations of the protocol have been demonstrated by >30 examples with yields up to 91%, showing a large electronic effect from the <i>N</i>-substituent in benzotriazinones. An unexpected steric acceleration has been observed from the core of benzotriazinones, not only promising a highly efficient access to 2-alkyl-2,3-disubstituted benzamides but also shedding light on the rate-limiting steps in the catalytic cycle. |
| format | Article |
| id | doaj-art-a36f79d55fef4f3588f786a1fd201880 |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj-art-a36f79d55fef4f3588f786a1fd2018802025-08-20T03:46:50ZengMDPI AGMolecules1420-30492025-05-013011239710.3390/molecules30112397Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl SulfonatesYingying Hong0Xuanxuan Zhang1Gang 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 Ni-catalyzed, Mn-mediated denitrogenative cross-electrophile coupling of <i>N</i>-alkyl-1,2,3-benzotriazinones with alkyl tosylates and mesylates for access to <i>o</i>-alkyl secondary benzamides is reported. The method uses inexpensive non-anhydrous dimethyl acetamide (DMA) in combination with tetrabutyl ammonium iodide (TBAI) as a co-catalyst to convert sulfonates into iodides in situ. Scope and limitations of the protocol have been demonstrated by >30 examples with yields up to 91%, showing a large electronic effect from the <i>N</i>-substituent in benzotriazinones. An unexpected steric acceleration has been observed from the core of benzotriazinones, not only promising a highly efficient access to 2-alkyl-2,3-disubstituted benzamides but also shedding light on the rate-limiting steps in the catalytic cycle.https://www.mdpi.com/1420-3049/30/11/2397cross-electrophile couplingnickel catalysisbenzotriazinonealkyl sulfonate |
| spellingShingle | Yingying Hong Xuanxuan Zhang Gang Zou Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates Molecules cross-electrophile coupling nickel catalysis benzotriazinone alkyl sulfonate |
| title | Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates |
| title_full | Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates |
| title_fullStr | Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates |
| title_full_unstemmed | Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates |
| title_short | Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates |
| title_sort | iodide nickel co catalyzed manganese mediated denitrogenative cross electrophile coupling of benzotriazinones with alkyl sulfonates |
| topic | cross-electrophile coupling nickel catalysis benzotriazinone alkyl sulfonate |
| url | https://www.mdpi.com/1420-3049/30/11/2397 |
| work_keys_str_mv | AT yingyinghong iodidenickelcocatalyzedmanganesemediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithalkylsulfonates AT xuanxuanzhang iodidenickelcocatalyzedmanganesemediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithalkylsulfonates AT gangzou iodidenickelcocatalyzedmanganesemediateddenitrogenativecrosselectrophilecouplingofbenzotriazinoneswithalkylsulfonates |