Oxidative Carbonylation of Alcohols and Amines

Oxidative carbonylation of alcohols using PdCl2 affords the carbonate 458 and the oxalate 459 [188,189]. Selectivity of the mono- and dicarbonylation depends on CO pressure and reaction conditions. 

Industrial processes for dialkyl oxalate and dimethyl carbonate from CO, alcohol and oxygen catalyzed by Pd have been developed by Ube Industries in Japan [2]. 

As an application, the polyoxalate 465 has been synthesized from dinitrite 464 using Pd-phosphine complex as a catalyst [190]. 

Dimethyl carbonate (467) is produced under low pressure CO. Dimethyl carbonate is now produced commercially by Ube industries based on the oxidative carbonylation of MeOH in the gas phase using methyl nitrite (466) as an oxidant as shown below. Another promising reaction is the preparation of commercially important diphenyl carbonate (468) by the oxidative carbonylation of phenol. So far the technology developed in many industrial laboratories is far from commercialization [191]. 

Oxidative carbonylation of amines affords alkylurea469 and oxamide 470 [192]. Substituted ureas were prepared efficiently in the presence of Pdl2 and KI under CO and CO2 pressure (total 60 atm) [193]. Synthesis of 2-oxazolidinone (471) by the carbonylation of 2-aminoethanol was carried out efficiently using a catalytic system of Pdl2-KI [194]. 

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