Synthesis and Versatile Utilization of2-PyridylandPyrimidyl-RelatedReagents

Active (thio)esters and amides were prepared from carboxylic acids and several reagents containing 2-pyridyl or pyrimidyl moiety. Active (thio)carbonates, thionocarbonate, and thiourea were prepared from (thio)phosgene and 2-hydroxypyridine or 2-mercaptopyridine. The acylation of active (thio)esters and amides containing 2-pyridyl or pyrimidyl groups with various organometallics afforded ketones, aldehydes, esters, amides, and beta-keto esters. The alkoxycarbonylation of active (thio)carbonates with Grignard reagents and amines afforded esters and carbamates, respectively. Active di(thiono)carbonates and thiourea containing the 2-pyridyl or pyrimidyl moiety have been used in the dehydration of carboxylic acids/alcohols or aldoximes, dehydrosulfurization of thioureas, and (thio)carbonyl transfer of diols or amines to produce esters or nitriles, carbodiimides, cyclic carbonates or isothiocyanates, respectively.