![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Palladium-Catalyzed C(sp2)-N Bond Cross-Coupling with Triaryl Phosphates
Zicong Chen1, Xiangmeng Chen1, Chau Ming So1,2
1Department of Applied Biology and Chemical Technology , The Hong Kong Polytechnic University , Hung Hom, Kowloon , Hong Kong.
The Journal of Organic Chemistry
|May 1, 2019
Summary
This study introduces a novel palladium-catalyzed method for aryl phosphate amination using MorDalPhos. This efficient catalytic system works with diverse amines and functional groups, enabling broad applications in organic synthesis.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Palladium-catalyzed cross-coupling reactions are crucial in organic synthesis.
- Aryl phosphates are versatile precursors, but their amination remains challenging.
- Development of efficient catalytic systems for aryl phosphate functionalization is needed.
Purpose of the Study:
- To describe the first general palladium-catalyzed amination of aryl phosphates.
- To develop a catalytic system effective for a wide range of substrates.
- To explore solvent-free and scalable reaction conditions.
Main Methods:
- Utilized a catalytic system comprising MorDalPhos and [Pd(π-cinnamyl)Cl]2.
- Investigated the amination of electron-rich, neutral, and electron-poor aryl phosphates.
- Tested reactions with aromatic, aliphatic, and heterocyclic amines.
- Evaluated compatibility with common functional groups (ether, keto, ester, nitrile).
- Performed solvent-free reactions with solid coupling partners.
- Demonstrated gram-scale synthesis.
Main Results:
- Achieved the first general palladium-catalyzed amination of aryl phosphates.
- The MorDalPhos/Pd catalyst system successfully aminated diverse aryl phosphates with various amines.
- Excellent functional group tolerance was observed for ether, keto, ester, and nitrile groups.
- Solvent-free amination was successful for solid reactants.
- Gram-scale synthesis was demonstrated, highlighting the system's practicality.
Conclusions:
- A novel and general palladium-catalyzed amination of aryl phosphates has been established.
- The developed catalytic system offers broad substrate scope and functional group tolerance.
- The method is amenable to solvent-free conditions and gram-scale synthesis, providing a valuable tool for organic chemists.
More Related Videos
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
10.2K
08:56Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
Published on: November 30, 2022
3.4K
Related Concept Videos
01:17Spin–Spin Coupling: One-Bond Coupling
1.4K
Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
1.4K
01:20Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
1.6K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.6K
01:22Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
1.5K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
1.5K
02:51Metal-Ligand Bonds
24.1K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
24.1K
02:49Bond Energies and Bond Lengths
31.3K
Stable molecules exist because covalent bonds hold the atoms together. The strength of a covalent bond is measured by the energy required to break it, that is, the energy necessary to separate the bonded atoms. Separating any pair of bonded atoms requires energy — the stronger a bond, the greater the energy required to break it.
31.3K
02:43Peptide Bonds
82.6K
A peptide bond covalently attaches amino acids through a dehydration reaction. One amino acid's carboxyl group and another amino acid's amino group combine, releasing a water molecule. The resulting bond is the peptide bond. The products that such linkages form are peptides. As more amino acids join this growing chain, the resulting chain is a polypeptide. Each polypeptide has a free amino group at one end. This end has the N-terminal, or the amino-terminal, and the other end has a free...
82.6K