| Title: |
Synthesis of Functionalized Homoallylic Alcohols via a Salt‐Free Three‐Component Nickel‐Catalyzed Coupling Reaction |
| Authors: |
Saint Pol, Anthony; Roger, Maxime; Mifleur, Alexis; Loxq, Pauline; Chausset‐boissarie, Laëtitia; Béthegnies, Aurélien; Penhoat, Maël; Suisse, Isabelle; Sauthier, Mathieu |
| Contributors: |
Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS); Université d'Artois (UA)-Centrale Lille-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS); Chimie Analytique et Réactivité Moléculaire En Normandie (Institut CARMeN); Université de Caen Normandie (UNICAEN); Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN); Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN); Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie); Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); Miniaturisation pour la Synthèse, l’Analyse et la Protéomique - UAR 3290 (MSAP); Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS); UCCS Équipe Chimie de Coordination et Catalyse pour la synthèse soutenable de Molécules, Macromolécules et Matériau (3C3M); Université d'Artois (UA)-Centrale Lille-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS) |
| Source: |
ISSN: 1615-4150. |
| Publisher Information: |
CCSD; Wiley-VCH Verlag |
| Publication Year: |
2025 |
| Collection: |
LillOA (HAL Lille Open Archive, Université de Lille) |
| Subject Terms: |
nickel; oxidative coupling; homogeneous catalysis; buitadiene; aldehyde; [CHIM.CATA]Chemical Sciences/Catalysis; [CHIM.ORGA]Chemical Sciences/Organic chemistry |
| Description: |
International audience ; In the presence of a catalytic amount (1 mol%) of Ni(cod) 2 and dppmb (1,2-bis(diphenylphosphinomethyl)benzene)), a three-component coupling reaction between industrially available aldehydes, buta-1,3-diene, and amines leads to the formation of variety of homoallylic alcohols with a highly functionalized 5-aminopent-3-en-1-ol structure. The reaction proceeds with 100% atom economy under mild conditions (80 °C) in isopropanol as solvent. The process accommodates both aliphatic and aromatic aldehydes in combination with cyclic and acyclic secondary dialkyl amines, demonstrating a broad substrates scope. Reaction monitoring shows that the initial rate of the reaction is 39 h -1 , and the process reaches a maximum within 3 h of reaction at 80 °C. A competitive reaction has been identified as the hydroamination of 1,3-butadiene that affords light butenylamines. The key mechanistic feature of the three-component nickel-catalyzed reaction is the formation of an η 3 :η 1 -allylalkoxy nickel (II) intermediate obtained from the oxidative coupling reaction between a low valent nickel (0) precursor, buta-1,3-diene, and an aldehyde. The amine subsequently reacts as a nucleophile with the electrophilic allyl moiety of this intermediate, while the alkoxy group acts as an internal base facilitating proton transfer that enables the synthesis of 5-aminopent-3-en-1-ol derivatives without any base and salt formation. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/adsc.70183 |
| Availability: |
https://hal.science/hal-05520865; https://hal.science/hal-05520865v1/document; https://hal.science/hal-05520865v1/file/adsc.70183.pdf; https://doi.org/10.1002/adsc.70183 |
| Rights: |
https://creativecommons.org/licenses/by/4.0/ ; info:eu-repo/semantics/OpenAccess |
| Accession Number: |
edsbas.F9066F4C |
| Database: |
BASE |