The Application Of Chiral Diamine/ruthenium Catalysts In Heterocyclic Synthesis And Dynamic Kinetic Resolution

It has found that aminopyran derivatives are play a important role in anti-allergy,anti-aging,reduces blood sugar levels,anticancer and anti-cell toxins activity.When the hydrogen in pyran ring was in place of amino and cyanide,it can became the synthon of some special natural product.Thanks to the aminopyran derivatives has important applications in medicine,the synthesis of this kind of compounds has attracted more and more attention.At present,there are few studies on chiral aminopyran compounds,and even fewer reports on the synthesis of chiral aminopyrans via asymmetric hydrogen transfer.Based on this,we synthesized a series of aminopyran derivatives via asymmetric hydrogen transfer.Benzoxaboroles,an important class of boron containing molecules,has recently acquired significant attention towards its applications for the development of new drugs.This leads to the development of benzoxaboroles with antibacterial,antiviral,anti-parasitic,anti-inflammatory,and antimalarial activities as well as?-lactamase inhibitor.At present,there are few reports of obtaining chiral benzoxaboroles through racemic resources.Therefore,our research start from the racemic resources and we have synthesized chiral benzoxaboroles with two chiral sites via dynamic kinetic resolution?DKR?-asymmetric transfer hydrogenation?ATH?.In the second chapter,a novel bifunctional Noyori-Ikariya type catalyst was developed,whichdisplaysgoodcatalyticefficiencyforMichael addition/ATH/cyclization tandem reaction of 1-phenylprop-2-en-1-one and malononitrile in H₂O/ⁱPrOH?1:3,v/v?at 60°C using HCOONa as a hydrogen source,providing a variety of chiral 3,4-dihydro-2H-pyran-5-carbonitriles in high yields?up to79%?with excellent enantioselectivities?up to 97%?.This method has the advantages of mild reaction conditions,simple operation and high yields.In the third chapter,a chiral?mesitylene?RuCl?monosulfonated diamine?catalyzed dynamic kinetic resolution?DKR?-asymmetric transfer hydrogenation?ATH?process was developed,which have been used in synthesis of a series of chiral?-hydroxyl benzoxaboroles via the reduction of racemic?-keto benzoxaboroles in MeOH at 60°C using HCOOH:Et₃N?5:2?as a hydrogen source with good yields?up to 73%?and highly enantioselectivities?up to 99%ee?and diastereoselectivities?up to 88:12 dr?.The structure of the products was characterized by ¹H-NMR,¹³C-NMR,HRMS and the enantioselectivity of the product was determined by HPLC.