Modification Of Chiral Phosphoric Acids Based On Binaphthol And Their Application In Asymmetric Catalytic Synthesis Of Axially Chiral Bisphenols

Axially chiral bisphenols are an important class of molecules with wide applications and high application value.In the field of asymmetric catalysis,these molecules can not only directly serve as chiral catalysts,but also be converted into various other chiral catalysts and ligands,and are widely used to catalyze a wide range of asymmetric reactions.For example,the derived chiral phosphoric acid catalyst can catalyze asymmetric Mannich reaction,Friedel-Crafts reaction,Diels-Alder reaction,cyclization reaction,ring opening reaction,conjugated addition reaction,etc.However,with the continuous development of asymmetric catalytic synthesis,the privileged catalysts derived from commonly used axially chiral bisphenols are difficult to obtain good reaction results in some asymmetric reactions,so it is necessary to further modify axially chiral bisphenols.The development of new axial chiral bisphenol frameworks and catalysts derived from them is urgent and of great research significance.The main contents of this thesis are as follows:(1)In view of the importance of chiral phosphoric acids based on the binaphthol skeletons,we performed a series of modifications on the 9-anthracene group at the 3,3’-position of chiral phosphoric acids based on the binaphthol skeletons,introduced a variety of substituents,and strictly regulated their electronic effect and steric effect through the change of substituents,and successfully synthesized a series of new 9-anthracene based chiral binaphthol phosphoric acid catalysts.(2)We designed chiral phosphoric acid-catalyzed desymmetric cyclization reaction of amphiphilic diaryltriphenols and propargyl alcohols,resulting in the synthesis of new axially chiral bisphenols(up to 97% yield,88:12 er).Compared with commonly used chiral phosphoric acid catalysts,our modified 9-anthracene based chiral binaphthol phosphoric acid catalysts can achieve better catalytic effect,higher reaction reactivity and better enantioselectivity.This protocol provides a simple and efficient synthetic strategy for the construction of axial chiral bisphenol frameworks.Compared with the BINOL structure,this new type of axial chiral bisphenol not only introduced heteroatom oxygen atom,but also owned more modified structural sites.They provided much more adjustable factors for their derived chiral phosphates,chiral phosphates,and chiral ligands,it is beneficial to extend the range of application and has great potential application prospects.