2023
DOI: 10.1021/acs.joc.3c00175
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Ru(II)-Catalyzed Regioselective Redox-Neutral [4 + 2] Annulation of N-Chlorobenzamides with 1,3-Diynes at Room Temperature for the Synthesis of Isoquinolones

Abstract: Herein, we report Ru(II)-catalyzed C–H/N–H bond functionalization of N-chlorobenzamides with 1,3-diynes via regioselective (4 + 2) annulation for the synthesis of isoquinolones under redox-neutral conditions at room temperature. This represents the first example of C–H functionalization of N-chlorobenzamides using an inexpensive and commercially available [Ru(p-cymene)Cl2]2 catalyst. The reaction is operationally simple, works in the absence of any silver additives, and is also applicable to a broad range of s… Show more

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Cited by 11 publications
(13 citation statements)
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“…This observation supports the experimental findings that the C−H activation step (I1 → I2) is not involved in the RDS, reflecting on the experimentally determined k H /k D value of 1.04. 5 Furthermore, the current computational mechanistic investigation along with the stepwise reaction energetics unambiguously support a Ru(II)/Ru(0)-type catalytic mechanism for the title reaction (Scheme 2).…”
Section: Reaction Energeticsmentioning
confidence: 53%
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“…This observation supports the experimental findings that the C−H activation step (I1 → I2) is not involved in the RDS, reflecting on the experimentally determined k H /k D value of 1.04. 5 Furthermore, the current computational mechanistic investigation along with the stepwise reaction energetics unambiguously support a Ru(II)/Ru(0)-type catalytic mechanism for the title reaction (Scheme 2).…”
Section: Reaction Energeticsmentioning
confidence: 53%
“…Evidently, the preferential binding of 1,3-diyne to the metal center in I4 along with the thermodynamic and kinetic favorability of the I5 intermediate is a clear reflection of the experimentally observed regioselectivity yielding the 3-alkynylated product (Figure ). Additionally, the insertion of the -yne moiety into the Ru–N bond in intermediate I4 (and I4′ ) is also considered. Based on the computed reaction energetics (see Supporting Information, Figure S1), the insertion of the -yne moiety into the Ru–N bond appears to be highly endergonic and leads to much higher energy intermediates (I5 N and I5 N ′) as compared to the insertion into the Ru–C bond ( I5 and I5′ ).…”
Section: Resultsmentioning
confidence: 99%
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“…Given that C–H bonds are ubiquitous in organic compounds, the direct and site-selective functionalization of C–H bonds to amend molecular complexity is tremendously attractive with respect to both step and atom economy. Despite the wide establishment of ortho -C­(sp 2 )–H functionalization, regioselective distal C–H functionalization is significantly more difficult because of the small differences in bond-dissociation energies of multiple C–H bonds. Recently, numerous methods have emerged that permit meta -C–H functionalization; , however, surprisingly, the development of para -selective C–H functionalization is limited.…”
Section: Introductionmentioning
confidence: 99%
“…For instance, the seminal works were reported by Beller and co-workers recently, in which they developed three elegant methods for highly selective dicarbonylation, monocarbonylation, and monohydroamidation of 1,3-diynes. In addition, 1,3-diynes could also serve as a good coupling partner in directing-group-assisted C–H activations in the presence of transition metals, such as Rh­(III), Co­(III), and Ru­(II) . Despite these significant contributions, the synthesis of complex polycyclic compounds via palladium­(II)-catalyzed polycyclization of 1,3-diynes is rarely reported.…”
mentioning
confidence: 99%