<scp>Palladium‐catalyzed</scp> C<b></b>H acetoxylation of arenes using a pyrazolonaphthyridine ligand

Kim, Jisu; Joo, Jung Min

doi:10.1002/bkcs.12599

Cited by 8 publications

(3 citation statements)

References 36 publications

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“…Recently, our group developed a series of pyrazole-containing ligands, including bicyclic pyrazolopyridine ( PzPy ) and tricyclic pyrazolonaphthyridine ( PzNPy ) derivatives, for Pd-catalyzed C–H functionalization (Figure B) . The incorporation of pyrazole, which is less Lewis basic than pyridine, into the electronically and sterically tailorable Pz(N)Py framework in a modular fashion offers opportunities to prepare electrophilic Pd(II) catalysts suitable for C–H cleavage at electron-rich and sterically accessible positions.…”

Section: Introductionmentioning

confidence: 99%

Nondirected Pd-Catalyzed C–H Perdeuteration and meta-Selective Alkenylation of Arenes Enabled by Pyrazolopyridone Ligands

et al. 2023

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The development of ligands and the elucidation of their roles in the catalytic cycle are key to achieving high efficiency and selectivity in nondirected transition-metal-catalyzed C–H functionalization. In particular, careful ligand design can enable the functionalization of previously inaccessible substrate positions, which can lead to regiodivergent transformations of common reactants. In this study, a series of pyrazolopyridone (PzPyOH) ligands that can be easily prepared in a single step was developed for the Pd-catalyzed perdeuteration and meta-selective alkenylation of arenes. In this system, the 2-pyridone moiety was incorporated to function as an internal base, facilitating C–H cleavage and rendering C–H activation reversible, even at challenging sp2 C–H bonds, thus enabling perdeuteration. In addition, the reversible activation of the C–H bonds implies that site selectivity is determined during the migratory insertion step in the alkenylation reaction, thereby preferentially functionalizing the meta-positions rather than the typically more reactive ortho- and para-positions of anisole derivatives. Further, the electronic and structural properties of the pyrazole moiety provide flexibility in the ligand binding to Pd, enabling the facile coordination of an alkene coupling partner during alkenylation. In this process, the hydrogen bonding between pyridone and acetate ligands was crucial to stabilize intermediates, allowing for different types of binding modes, including L,L- and L,X-type bidentate and monodentate binding. Kinetic and computational studies support the proposed mechanisms for perdeuteration and alkenylation, and the findings reveal crucial factors in the design of ligands for Pd-catalyzed C–H functionalization, which will be useful for further development of pyrazole- and pyridone-containing ligands in transition metal catalysis.

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Section: Introductionmentioning

confidence: 99%

Nondirected Pd-Catalyzed C–H Perdeuteration and meta-Selective Alkenylation of Arenes Enabled by Pyrazolopyridone Ligands

et al. 2023

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“…In a continuation of our ongoing study related to B–H and C–H functionalization, we wondered if sulfoxonium ylide could be used as a directing group for functionalization of o -carborane, whether multifunctionalization was possible because it was stable, and whether it could be converted to other functional groups after reaction. In this study, we described an Ir(I)-catalyzed regioselective B(4)-alkenylation reaction from o -carboranyl sulfoxonium ylides and alkynes through B(4)–H activation ( f ).…”

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Iridium-Catalyzed Regioselective B(4)-Alkenylation and B(3,5)-Dialkenylation of o-Carboranes

Noh,

Kim,

Lee

et al. 2023

Org. Lett.

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Iridium(I)-catalyzed regioselective B(4)-alkenylation has been developed from o-carboranyl sulfoxonium ylides and alkynes through B(4)−H activation. The sequential B(4)-and B(6)-alkenylation afforded B(3,5)-dialkenylated o-carboranyl sulfoxonium ylides in one pot. Eventually, two alkenyl groups, the same or different, were introduced at positions 3 and 5 of the carborane. Sulfoxonium ylide used as a directing group remains available for further functionalization and is converted to Balkenylated o-carboranyl trichloromethyl ketones.

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“…25,26 Recently, we had developed a series of pyrazolopyridine (PzPy) and pyrazolonaphthyridine (PzNPy) ligands for the nondirected C-H functionalization of electron-rich (hetero)arenes. [27][28][29][30][31] Based on these results, we envisioned the C-H alkenylation of RcH and FcH using electrophilic Pd(II) complexes derived from these Pz(N)Py ligands. In this process, it was anticipated that the stable bidentate binding mode of these ligands would allow the oxygenpromoted reoxidation of Pd(0).…”

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confidence: 99%

Nondirected Pd-catalyzed aerobic C–H alkenylation of ruthenocene and ferrocene

et al. 2022

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Palladium‐catalyzed CH acetoxylation of arenes using a pyrazolonaphthyridine ligand

Cited by 8 publications

References 36 publications

Nondirected Pd-Catalyzed C–H Perdeuteration and meta-Selective Alkenylation of Arenes Enabled by Pyrazolopyridone Ligands

Nondirected Pd-Catalyzed C–H Perdeuteration and meta-Selective Alkenylation of Arenes Enabled by Pyrazolopyridone Ligands

Iridium-Catalyzed Regioselective B(4)-Alkenylation and B(3,5)-Dialkenylation of o-Carboranes

Nondirected Pd-catalyzed aerobic C–H alkenylation of ruthenocene and ferrocene

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