52798-94-4

Upstream product

• 201230-82-2 carbon monoxide 
• 93087-35-5 4-iodobenzoic acid phenyl ester 
• 1864-94-4 phenyl formate 
• 15164-44-0 p-(iodophenyl)carboxaldehyde 
• 619-66-9 4-Carboxybenzaldehyde 
• 102-09-0 bis(phenyl) carbonate 
• 108-95-2 phenol 

Downstream Products

• 1143504-70-4 C₂₈H₂₂O₆ 
• 492-70-6 1,2-diphenyl-1,2-ethanediol 
• 864447-44-9 C₉₉H₈₆Cl₂N₈O₃₂ 

Relevant academic research and scientific papers

Mechanistic Insight into Weak Base-Catalyzed Generation of Carbon Monoxide from Phenyl Formate and Its Application to Catalytic Carbonylation at Room Temperature without Use of External Carbon Monoxide Gas

The mechanisms of the weak base-catalyzed generation of carbon monoxide (CO) and phenol from phenyl formate were investigated by experimental and theoretical methods. Kinetic studies revealed a first-order reaction in both phenyl formate and the base. The reaction was found to proceed by an E2 α-elimination pathway, which involves the abstraction of the formyl proton of phenyl formate, simultaneously generating CO and phenoxide. The reaction rate was affected by the substituents on phenyl formate, the polarity of solvents, and the basicity of bases. The mechanistic insight obtained from these studies permitted the chemical control of the rate of CO generation, which was the key to the development of the external CO-free Pd-catalyzed phenoxycarbonylation of haloarenes at room temperature. Because of the mild reaction conditions and wide substrate scope, this phenoxycarbonylation constitutes a general, safe, and practical method to synthesize arenecarboxylic acid esters. (Figure presented.).

Metal-Free O-Arylation of Carboxylic Acid by Active Diaryliodonium(III) Intermediates Generated in situ from Iodosoarenes

The metal-free arylative coupling of carboxylic acids using iodosoarenes without the use of a catalyst and base, which is applicable to even a highly-polar molecule bearing multiple alcohol groups, is reported. The in situ preparation of the reactive diaryliodonium(III) carboxylates is the important key to this approach, and the introduction of the trimethoxybenzene auxiliary enables both the smooth salt formations and the selective aryl transfer events during the couplings. (Figure presented.).

Ligandless Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides under Ambient Conditions

Ligandless palladium-catalyzed reductive carbonylation of aryl iodides for the synthesis of aromatic aldehydes has been developed. This carbonylation process proceeded effectively even under ambient temperature and pressure. In addition, this method enables successive reductive carbonylation of diiodobenzenes to furnish dialdehydes in satisfactory yields. Finally, the nature of the active catalytic species is discussed.

Base catalyzed sustainable synthesis of phenyl esters from carboxylic acids using diphenyl carbonate

Phenyl esters were obtained in moderate to high yields by reaction of aliphatic and aromatic carboxylic acids with one equivalent of diphenyl carbonate in the presence of catalytic amounts of tertiary amine bases, such as DBU, TBD and DMAP under neat conditions at elevated temperatures (>100°C).

Palladacycle-catalyzed carbonylation of aryl iodides or bromides with aryl formates

An efficient palladacycle-catalyzed aromatic carbonylation reaction of aryl formates with aryl iodides or bromides has been developed. Commercially available and easily prepared aryl formates were employed as carbonyl sources without the use of external carbon monoxide. The present catalytic system shows broad functional group tolerance and affords aryl benzoate derivatives in good to excellent yields. Copyright

Palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides with phenyl formate

Highly efficient palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides with phenyl formate is reported. This procedure does not use carbon monoxide and affords one-carbon-elongated carboxylic acid phenyl esters in excellent yields. The reaction proceeds smoothly under mild conditions and tolerates a wide range of functional groups including aldehyde, ether, ketone, ester, and cyano groups. Furthermore, a variety of heteroaromatic bromides can be converted to the corresponding phenyl esters in high yields.

Palladium-catalyzed esterification of aryl halides using aryl formates without the use of external carbon monoxide

Aryl formates are efficient carbon monoxide sources in palladium-catalyzed esterification of aryl halides. The carbonylation readily proceeds at ambient pressure without the use of external carbon monoxide to afford the corresponding esters in high yields.