Skeletal Transformation Of Oxindoles Into Quinolinones Enabled By Synergistic Copper/Iminium Catalysis

The synergistic catalytic mode has overcome the limitations of traditional single catalytic mode,and effectively reduced the reaction energy barrier,which has achieved rapid development in recent years.Up to now,chemists have developed several synergistically catalytic strategies such as bi-metallic catalysis,metal-organo catalysis,and organo-organo catalysis.In this context,synergistic transition metal-organo catalysis has been flourished into a highly significant and useful strategy in chemical synthesis,where the complementary modes of substrate activation would bring about novel type of transformations,or improve efficiency,chemo-,regio-,and stereoselectivity of known reactions.In addition,modification of the underlying molecular skeleton(skeletal editing)represents a considerably fascinating and useful strategy to convert readily accessible compounds into other molecules with totally distinct core skeletons,which is also important for drug development and research on functional materials.Considering the synthetic merits of the transition metal-iminium synergistic catalysis and skeletal editing,we envisioned to develop novel methods merging such two strategies for the facile transformation of easily accessible compounds into other important molecules that would not be accessed in a concise manner.We disclose a Cu/secondary amine-catalyzed skeletal editing protocol using readily available isatinderived enals and oxime esters as the starting materials for the rapid conversion of oxindole core into quinolinone skeleton.At the same time,we retain the lactam part of oxindole,rapidly construct one C-N bond,one C-C bond and one C=C bonds,and further transform the indigo skeleton into a pyridine fused quinolinone skeleton.This dissertation is mainly divided into three parts: the first chapter is a literature review of synergistic metal-organo catalysis;the second and the third parts are experimental sections,which describe the optimization process of reaction conditions,substrate scope of the reactions,and data characterization of the related compounds.