Research On New Method For Synthesis Of Chiral IDPA And The Construction Of Chiral Tertiary Alcohols And Their Participation In The Reactions

The chiral IDPAs have good structure rigidity and compact chiral cavity owing to their special skeletons,they showed excellent chiral controllability in a variety of catalytic asymmetric reactions.This paper discussed a new method for the synthesis of chiral IDPA,we applied this type of catalyst to the synthesis for chiral tertiary alcohols,and we also studied the synthetic reaction with the tertiary alcohols as a component.Chapter 1:Firstly,the asymmetric catalytic reactions with the biaxial chiral IDPA as catalyst was introduced to illustrate their importance in the asymmetric catalysis field.Secondly,we summarized the synthetic method of chiral tertiary alcohols and the present research progress.Finally,we make an introduction of a series of reactions with the tertiary alcohols taking participate briefly.Chapter 2:We developed a new method for the synthesis of catalysts successfully.We used the Kumada coupling reaction instead of the commonly used Suzuki coupling reaction synthesis for 3,3' functionalized H8-BINOL with high yield and low cost.In this method,we use Br-H8-BINOL as starting materials,after hydroxyl protecting,Kumada coupling and deprotection,about six major steps in the synthesis of H8-BINOL-IDPA catalyst with an increased yield to 45%.This approach also applies to the catalyst with other substituents in 3,3' position.Chapter 3:We introduced highly enantioselective Friedel–Crafts reactions of indoles with isatins catalyzed by Chiral Imidodiphosphoric Acids synthesis for 3-hydroxyl-3-indolyloxindoles with tertiary alcohols group.Optimal conditions were obtained after a series screening of catalysts,solvents and additives,25 instances was extended with high yields up to 98% and as high as 99% ee.We have increased the reaction rate and reduce the catalyst loadings to 2 mol% comparing to other types of chiral catalysts,Br?nsted acid catalysts applied in this reaction was realized first time.Chapter 4:We introduced highly enantioselective Friedel-Crafts reactions of phenols with isatins catalyzed by Chiral Imidodiphosphoric Acids synthesis for the tertiary alcohols.We firstly have condition screened used sesamol as basic substrate,we obtained the optimal reaction conditions after a series screening of catalysts,solvents and additives with as low as 2 mol% catalyst loadings.With optimal conditions in hand,we extended 14 instances with high yields up to 95% and as high as 92% ee.Then we test different substituents of isatins with 6-hydroxy-1,4-benzodioxane as basic substrate,extended 11 instances with high yields up to 93% and as high as 95% ee.The blank of phenols with isatins catalyzed by chiral Br?nsted acid synthesis for the tertiary alcohols was filled up ultimately.Chapter 5:We obtained bioactivity 3,3'-biindolin-2-ones via reduction reaction with 3-hydroxyl-3-indolyloxindoles as reactant.After the determination of benzothiazoline as reducing agent,we got the optimal reaction conditions;the reaction proceeds smoothly under mild conditions and is applicable to a broad scope of substrates.We extended 21 instances with high yield up to 99%.Achieved the goal for the synthesis of 3,3'-biindolin-2-ones without metals,enriched the content of the reactions with tertiary alcohols as components.