Organopalladium approaches to interphenylene prostaglandin analogs, heterocycles and carbocycles

摘要

This dissertation is divided into three parts. Each part in itself is suitable for publication. The focus of this dissertation will be organopalladium approaches to (a) interphenylene prostaglandin analogs, (b) nitrogen and oxygen heterocycles and (c) carbocycles;The first part will discuss the synthesis of prostaglandin analogs. Three new interphenylene prostaglandin analogs have been synthesized using a novel one pot, organopalladium approach. The strategy involves the addition of both the benzylic side chain (containing the carboxylic acid unit) and the acetylenic side chain to a symmetrical bridged, bicyclic olefin, such as norbornene, in the presence of catalytic amounts of a palladium(0) complex. Model system studies, as well as attempts to synthesize other novel interphenylene prostaglandin analogs are described;The second part will discuss the synthesis of heterocycles, such as indoles, quinolines, isoquinolines and benzopyrans. This strategy involves the intramolecular addition of arylpalladium compounds to olefinic bonds leading to the aforementioned heterocycles. Though this approach has been examined by other chemists, we decided to modify the reaction by introducing a phase transfer reagent. As a result, out reactions proceed at lower temperatures and give higher product yields;Intramolecular addition of arylpalladium compounds to olefinic bonds leading to carbocycles is described in the final section.