The Methodology Research On Structural Modification Of ?-aminoketones

?-Amino carbonyl motif is ubiquitous subunit in biologically active natural products,biomolecules and therapeutic agents.?-Aminoketone has significant chemical reaction sites,and the conversions of its derivatives also provide straightforward and rapid access to many biological active compounds.?-Aminoketone is also an important synthetic block in organic synthesis.For these reasons,the transformations of?-amino carbonyl derivatives have been a longstanding hot topic in organic and bioorganic syntheses.In this paper,we have developed structural transformation of cyclic and chain?-amino compounds,respectively.The specific studies are as followed:1.At 90?,a novel tert-butyl hydroperoxide?TBHP?promoted CH₂-extrusion reaction of cyclic?-amino carbonyl compound has been developed,which is driven by an demethylenation process to give various ring contraction products?-lactams.The reaction shows good functional group tolerance and excellent atom economy,all the desired products are obtained in moderate to excellent yields.It provides a new method for the simple and efficient preparation of?-lactams.2.At 110?,chain?-amino compounds react with TBHP to obtain corresponding?-ketone esters in 52%-78%yield.More significantly,we also found that different esterification products can be obtained by using different peroxides?such as cumene hydroperoxide?.This reaction provides a simple and efficient route to synthesize different substituted?-ketone esters from?-amino carbonyl compounds.