Transition-Metal-Catalyzed Transformations Of Phenolic Derivatives By Using A Cooperative C-H Bond Activation/Arene Dearomatization Approach

The ubiquitous phenols are a class of cheap chemical feedstock being widely utilized in a plethora of natural products and functional skeletons,which have been prepared from these readily available starting materials.In recent years,enriching the reaction styles and proceeding diversified developments of phenolic compounds has become an important research in organic synthetic chemistry.Meanwhile,in order to comply with the development requirements of green chemistry,it has been one of the important tasks presented by the current green chemistry that exploring the new synthetic methods being of effectivity,conciseness,economy and greenness and realizing the convenient transformation and utilization of these compounds furtherly.Therefore,this thesis is closely focused on the derivative ways of phenolic compounds and committed to the cooperative activation of inert C-H bond and stable aromatic rings,aiming to explore more concise and practical transforming ways of phenols.The chapter one mainly describes that the two new-style chemical reaction modes of phenol compounds are systematically centred on C-H bond activation and dearomatization reactions,which demonstrates the various derivative styles of these compounds detailedly in recent years.The chapter two presents a novel organic reaction on spiroannulation of naphthol compounds by using a copperative C-H bond activation/dearomatization approach.A series of spirocyclic skeletons existed widely in various biologically active natural products and optoelectronic materials could be obtained by the successful vinylative spiocyclization of naphthols that utilizes phenol hydroxyl as the weak directing group and alkyne as coupling reagent via ruthenium catalyst.The third chapter continues to depict an efficient organic reaction on spiroannulation and polycyclization of phenol-derived halogenated biaryls by the above strategy.This transformation employs bromoalkyl alkynes as coupling partner and adopts Catellani domino reaction style to afford a variety of complex spirocyclic molecules,which realizes the remote C-H bond activation and arene dearomatization approach of phenol-derived halogenated biaryls with excellent chemoselectivity because of preventing kinds of by-products from generating by controling the reaction condition accurately.In chapter four,an introduction on a new method producing chiral a-aminoketone compounds is provided.Regulated by Sc(OTf)3/Pybox catalyst,this method takes azodicarboxylates as electrophile to prepare a multitude of chiral a-aminoketone molecules containing a nitrogen-containing quaternary carbon in nearly 100%by the catalytic asymmetric aminative dearomatization of 1-substituted 2-naphthols,which could be efficient to conduct scaled-up experiment and able to cut the dosage of catalyst to 1 mol%.