| Title: |
(P,N,P)Pd‐versus (P,N,P)Ni‐Catalyzed Suzuki‐Miyaura Cross‐Coupling Reactions under Green Conditions |
| Authors: |
Fagué, Vincent; dos Santos, Diogo; Daran, Jean‐claude; Mallet‐ladeira, Sonia; Guillo, Pascal; Fliedel, Christophe |
| Contributors: |
Laboratoire de chimie de coordination (LCC); Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Université de Toulouse (EPE UT); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut de Chimie de Toulouse (ICT); Institut de Recherche pour le Développement (IRD)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS); Institut de Chimie de Toulouse (ICT); Communauté d'universités et établissements de Toulouse (Comue de Toulouse); Plateforme technologique et d'expertise de l'Institut de chimie de Toulouse (ICT-PTE); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); CNRS; ANR-22-CE07-0029,NiCatEther,Réactions de couplages catalysées au nickel : un grand pas vers un accès écoresponsable aux éthers(2022) |
| Source: |
ISSN: 1434-1948. |
| Publisher Information: |
CCSD; Wiley-VCH Verlag |
| Publication Year: |
2025 |
| Collection: |
Université Toulouse III - Paul Sabatier: HAL-UPS |
| Subject Terms: |
Nickel; Green reaction conditions; Small bite angle ligand; Suzuki-Miyaura Cross-coupling; Catalysis; Phosphine; Palladium; [CHIM.COOR]Chemical Sciences/Coordination chemistry; [CHIM.CATA]Chemical Sciences/Catalysis; [CHIM.CRIS]Chemical Sciences/Cristallography; [CHIM.ORGA]Chemical Sciences/Organic chemistry |
| Description: |
International audience ; Palladium dichloride (6‐10) and nickel dichloride (11‐15) complexes of a series of N-‐substituted/functionalized bis(diphenylphosphino)amine‐type ligands (1‐5 ) were synthesized and characterized, using multinuclear NMR and FT‐IR spectroscopic techniques, mass spectrometry and elemental analysis. The solid‐state structures of two palladium(II) ( 6 and 8⋅2CHCl 3 ) and two nickel(II) (12 and 15) complexes could be confirmed by single‐crystal X‐ray diffraction studies. All the complexes were evaluated as catalysts in the Suzuki‐Miyaura cross‐coupling reaction. Applying what appeared, from the literature, as the optimized reaction conditions for such complexes, i. e . Cs 2 CO 3 as base and 1,4‐dioxane as solvent, the palladium catalysts were found very efficient for the coupling of phenylboronic acid and aryl bromides functionalized with weak and moderate electron donating groups (EDGs) and weak and moderate electron withdrawing groups (EWGs). In contrast, reduced activity was observed for aryl bromides functionalized with strong EDGs and EWGs and no activity for aryl chlorides. Under the same reaction conditions, the nickel catalysts were completely inactive. Applying different and “greener” reaction conditions, i. e . K 3 PO 4 as base and tert ‐amyl alcohol as solvent, the nickel catalysts efficiently converted various aryl bromides and chlorides with a pool of aryl boronic acids, therefore clearly surpassing their palladium analogues at lower cost, economically and environmentally. Surprisingly, these reaction conditions could also be successfully applied to the palladium complexes, improving their performances (activity towards aryl chlorides) and offering a “greener” alternative to the common conditions. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/ejic.202400729 |
| Availability: |
https://hal.science/hal-04939963; https://hal.science/hal-04939963v1/document; https://hal.science/hal-04939963v1/file/Fagu%C3%A9,%20P%20N%20P%20Pd%E2%80%90%20versus%20P%20N%20P%20Ni%E2%80%90Catalyzed%20Suzuki%E2%80%90Miyaura%20Cross%E2%80%90Coupling%20Reactions,%202025.pdf; https://doi.org/10.1002/ejic.202400729 |
| Rights: |
http://creativecommons.org/licenses/by-nc-nd/ ; info:eu-repo/semantics/OpenAccess |
| Accession Number: |
edsbas.8C78C893 |
| Database: |
BASE |