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Peer-reviewedCC BYAngewandte Chemie International Edition

Unlocking Catalyst Activation as a Critical Bottleneck in Cross‐Coupling Reactions: Room‐Temperature Couplings of Weak Nucleophiles Enabled by [Pd(1‐MeNAP)TFA] 2 Precatalysts

  • Sourav Manna1
  • Henric F. Janning1
  • Nikolaos V. Tzouras1
  • Jane Anto Simplica Sagayaraj1
  • Fadil Faizal Mannighayil1
  • Angelino Doppiu2
  • Lukas J. Gooßen1
  1. 1Chair of Organic Chemistry I, Faculty of Chemistry and Biochemistry Ruhr‐Universität Bochum Bochum Germany
  2. 2Precious Metals Chemistry Umicore AG & Co. KG Hanau‐Wolfgang Germany
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Abstract

The trifluoroacetate‐bridged methylnaphthyl complex [Pd(1‐MeNAP)TFA] 2 is introduced as a bench‐stable, highly soluble palladium source that consistently delivers exceptional catalytic activity. It reacts within minutes with even the most sterically demanding ligands to form monoligated Pd complexes and, upon exposure to nucleophiles, including weak, non‐reducing N ‐nucleophiles, rapidly generates reactive Pd(0) species with the release of inert naphthalene derivatives. Across 15 representative transformations, catalysts generated in situ from [Pd(1‐MeNAP)TFA] 2 enable substantial reductions in reaction temperature, often by 80°C, while preserving established ligands and reaction conditions, thereby providing a drop‐in solution to existing reactivity limitations. As a result, arylations of amides, carbamates, sulfonamides, amidines, ureas, cyclopropylamines, and trifluoroethylamines can be performed at room‐temperature with markedly improved functional‐group tolerance and compatibility with sensitive, coordinating heterocycles. Mechanistic studies reveal that catalyst activation, rather than catalytic turnover, has been the principal bottleneck in many cross‐coupling reactions.

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Cite

BibTeXRIS
BibTeX
@article{manna2026unlocking,
  title = {{Unlocking Catalyst Activation as a Critical Bottleneck in Cross‐Coupling Reactions: Room‐Temperature Couplings of Weak Nucleophiles Enabled by [Pd(1‐MeNAP)TFA] 2 Precatalysts}},
  author = {Sourav Manna and Henric F. Janning and Nikolaos V. Tzouras and Jane Anto Simplica Sagayaraj and Fadil Faizal Mannighayil and Angelino Doppiu and Lukas J. Gooßen},
  journal = {Angewandte Chemie International Edition},
  year = {2026},
  month = may,
  doi = {10.1002/anie.3359287},
  url = {https://doi.org/10.1002/anie.3359287},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Unlocking Catalyst Activation as a Critical Bottleneck in Cross‐Coupling Reactions: Room‐Temperature Couplings of Weak Nucleophiles Enabled by [Pd(1‐MeNAP)TFA] 2 Precatalysts
AU  - Sourav Manna
AU  - Henric F. Janning
AU  - Nikolaos V. Tzouras
AU  - Jane Anto Simplica Sagayaraj
AU  - Fadil Faizal Mannighayil
AU  - Angelino Doppiu
AU  - Lukas J. Gooßen
PY  - 2026
DA  - 2026/05/13
JO  - Angewandte Chemie International Edition
DO  - 10.1002/anie.3359287
UR  - https://doi.org/10.1002/anie.3359287
AB  - The trifluoroacetate‐bridged methylnaphthyl complex [Pd(1‐MeNAP)TFA] 2 is introduced as a bench‐stable, highly soluble palladium source that consistently delivers exceptional catalytic activity. It reacts within minutes with even the most sterically demanding ligands to form monoligated Pd complexes and, upon exposure to nucleophiles, including weak, non‐reducing N ‐nucleophiles, rapidly generates reactive Pd(0) species with the release of inert naphthalene derivatives. Across 15 representative transformations, catalysts generated in situ from [Pd(1‐MeNAP)TFA] 2 enable substantial reductions in reaction temperature, often by 80°C, while preserving established ligands and reaction conditions, thereby providing a drop‐in solution to existing reactivity limitations. As a result, arylations of amides, carbamates, sulfonamides, amidines, ureas, cyclopropylamines, and trifluoroethylamines can be performed at room‐temperature with markedly improved functional‐group tolerance and compatibility with sensitive, coordinating heterocycles. Mechanistic studies reveal that catalyst activation, rather than catalytic turnover, has been the principal bottleneck in many cross‐coupling reactions.
SN  - 1433-7851
SN  - 1521-3773
ER  -