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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| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-05-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/11/2397 |
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| Summary: | 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. |
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| ISSN: | 1420-3049 |