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Decarbonylative C-P Bond Formation Using Aromatic Esters and Organophosphorus Compounds
Ryota Isshiki1, Kei Muto1, Junichiro Yamaguchi1
1Department of Applied Chemistry, Waseda University , 3-4-1 Ohkubo, Shinjuku, Tokyo 169-8555, Japan.
Organic Letters
|February 3, 2018
Summary
Nickel catalysis enables C-P bond formation using aromatic esters as novel aryl sources, facilitated by a thiophene-based diphosphine ligand (dcypt). This method efficiently synthesizes aryl phosphorus compounds from esters and phosphine oxides or phosphates.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Developing efficient methods for carbon-phosphorus (C-P) bond formation is crucial in synthetic chemistry.
- Traditional C-P bond formation often requires specific precursors or harsh conditions.
- Aromatic esters are typically not employed as arylating agents in C-P coupling reactions.
Purpose of the Study:
- To establish a novel nickel-catalyzed protocol for C-P bond formation.
- To utilize aromatic esters, including heteroaromatics, as unconventional aryl sources.
- To demonstrate the broad applicability and synthetic utility of the developed method.
Main Methods:
- Employing a nickel catalyst in combination with a thiophene-based diphosphine ligand, denoted as dcypt.
- Reacting various aromatic esters with phosphine oxides or phosphates under optimized catalytic conditions.
- Investigating the scope of the reaction with different ester substrates and phosphorus sources.
Main Results:
- Successful formation of C-P bonds using aromatic esters as arylating agents.
- Identification of the thiophene-based diphosphine ligand (dcypt) as critical for the catalytic activity.
- Coupling of diverse aromatic esters, including heteroaromatics, with phosphine oxides and phosphates to yield aryl phosphorus compounds.
- Demonstration of the method's utility through sequential coupling reactions.
Conclusions:
- A novel and efficient Ni-catalyzed method for C-P bond formation has been developed.
- Aromatic esters serve as effective and unconventional aryl sources in this transformation.
- The use of the dcypt ligand is key to achieving high yields and broad substrate scope.
- The protocol offers a valuable tool for synthesizing aryl phosphorus compounds and enables sequential coupling strategies.
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