681-02-7

Upstream product

• 3790-23-6 tetraethyldiphosphine disulfide 
• 701-53-1 p-methoxybenzoyl fluoride 
• 1536-23-8 2,3,4,5,6-pentafluorobenzophenone 
• 1251445-57-4 diethyl(4-(dimethylamino)benzoyl)phosphine sulfide 

Relevant academic research and scientific papers

Equilibrium shift in the rhodium-catalyzed acyl transfer reactions

Rhodium/phosphine complexes catalyze equilibrium acyl transfer reactions between acid fluorides, aryl esters, acylphosphine sulfides, and thioesters. The use of appropriate co-substrates to accept heteroatom groups shifted the equilibrium to desired products. Acylphosphine sulfides and aryl esters were converted to acid fluorides using benzoylpentafluorobenzene as the fluoride donor, and the fluorination reaction of thioesters employed (4-tolylthio) pentafluorobenzene. Acid fluorides were converted into acylphosphine sulfides and thioesters using diphosphine disulfides and disulfides/triphenylphosphine, respectively. Aryl esters were obtained from acid fluorides and phenols in the presence of triphenylsilane. Aryl esters, acylphosphine sulfides, and thioesters were also interconverted in the presence of rhodium complexes. These rhodium-catalyzed acyl transfer reactions proceeded under neutral conditions without using acid or base. The involvement of acyl rhodium intermediates in these reactions was suggested by the carbothiolation reaction of thioesters and alkynes.

Synthesis of acylphosphine sulfides by rhodium-catalyzed reaction of acid fluorides and diphosphine disulfides

A rhodium complex catalyzed the reaction of acid fluorides and tetraethyldiphosphine disulfide giving acylphosphine sulfides. Aromatic acid fluorides with electron donating p-groups reacted smoothly giving the products in high yields. Aliphatic acid fluorides with secondary and tertiary a-carbons were also converted to alkanoylphosphine sulfides, whereas the reaction of a substrate with an α-methylene carbon was accompanied by enol ester formation.