Palladium‐Catalyzed γ‐Arylation of Acylketene Synthons with Aryl Chlorides Enabled by Ylide‐Functionalized Phosphines (YPhos)

Manna, Sourav; Papp, Florian; Hisata, Yusei; Löffler, Julian; Rybka, Martyna; Gessner, Viktoria H.; Hoshimoto, Yoichi; Gooßen, Lukas J.

doi:10.1002/adsc.202301474

“…We have recently introduced methylnaphthyl (MeNAP) Pd complexes as easy-to-use catalyst precursors with a high activity in various cross-coupling reactions . In combination with bulky, electron-rich AdBrettPhos, [Pd(2-MeNAP)Br] 2 efficiently promotes the monoarylation of ammonium triflate with aryl chlorides with exceptional selectivity within short reaction times .…”

Section: Introductionmentioning

confidence: 99%

Pd-Methylnaphthyl-^tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Xue,

Papp,

Yang

et al. 2024

ACS Catal.

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Only a few sterically crowded ligands promote palladium-catalyzed, selective monoarylations of ammonia and hydrazine. We herein demonstrate that the formation of palladium precatalysts bearing such ligands is the limiting factor in these reactions, and we present bench-stable, Pd-methylnaphthyl (MeNAP)-t BuBrettPhos complexes as effective catalysts. X-ray and spectroscopic analyses have revealed that the biaryl system of the ligand reversibly inserts into the Pd-(MeNAP)C bond during complex formation. The performance of MeNAP complexes is shown to be a consequence of their clean formation and rapid activation. Their preparative utility is demonstrated by the synthesis of 32 anilines and arylhydrazines.

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Kopplung von Arylchloriden mit Lithium‐Nukleophilen, an molekular definierten Alkynyllithium‐Palladium‐Katalysatoren

Goebel,

Stemmer,

Krüger

et al. 2024

Angewandte Chemie

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Palladium‐catalyzed cross‐couplings of aryl chlorides usually call for bulky, electron‐rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross‐coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li‐alkynyl‐Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl‐, alkyl‐, and allyllithium compounds as well as lithium amines. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

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Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts

Goebel,

Stemmer,

Krüger

et al. 2024

Angew Chem Int Ed

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Palladium‐catalyzed cross‐couplings of aryl chlorides usually call for bulky, electron‐rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross‐coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li‐alkynyl‐Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl‐, alkyl‐, and allyllithium compounds as well as lithium amines. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

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Palladium‐Catalyzed γ‐Arylation of Acylketene Synthons with Aryl Chlorides Enabled by Ylide‐Functionalized Phosphines (YPhos)

Cited by 3 publications

References 49 publications

Pd-Methylnaphthyl-^tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Pd-Methylnaphthyl-^tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Kopplung von Arylchloriden mit Lithium‐Nukleophilen, an molekular definierten Alkynyllithium‐Palladium‐Katalysatoren

Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts

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Palladium‐Catalyzed γ‐Arylation of Acylketene Synthons with Aryl Chlorides Enabled by Ylide‐Functionalized Phosphines (YPhos)

Cited by 3 publications

References 49 publications

Pd-Methylnaphthyl-tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Pd-Methylnaphthyl-tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Kopplung von Arylchloriden mit Lithium‐Nukleophilen, an molekular definierten Alkynyllithium‐Palladium‐Katalysatoren

Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts

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Product

Resources

About

Pd-Methylnaphthyl-^tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine

Pd-Methylnaphthyl-^tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine