Development of Carbonylative Generation of Ketene and Its Application to the Synthesis of Useful Compounds

开发了一种新的潜在的烯基烯酮类化合物，不使用羧酸或活性衍生物制备。在CO压力下，钯催化的磷酸烯丙基酯在亚胺和叔胺存在下的羰基化反应高产率地立体选择性地合成了顺式或反式-3-烯基-1-β-内酰胺。立体化学结果很大程度上取决于所使用的亚胺的性质。与酮或酯等羰基偶联的亚胺在室温下立体选择性地生成顺式-β-内酰胺，而未与羰基偶联的亚胺在70ﾟC下唯一地生成反式-β-内酰胺。

A new potential alkenylketene equivalent, prepared without use of a carboxylic acid or an activated derivative, has been exploited. Palladium-catalyzed carbonylation of an allyl phosphate in the presence of an imine and a tertiary amine under CO pressure (30Kgcm^<-2>) stereoselectively gave either a cis-or trans-3-alkeny1-beta-lactam in high yield. The stereochemical outcome strongly depends on the nature of the imine employed. Imines conjugated with a carbonyl such as a ketone or an ester stereoselectively produce cis-beta-lactams at room temperature, whereas imines unconjugated with a carbonyl group exclusively afford trans-beta-lactams at 70ﾟC.