Organocatalyzed Asymmetric Synthesis Of Propargylamines

Propargylamines are a class of synthetically useful and versatile building blocks for the synthesis of polyfunctional amino derivatives,natural products and biologically active compounds.Therefore,the development of the simple and effective synthetic strategies for the assymbly of propargylamine compounds has drawn much attention from many organic synthetic chemists.This article focuses on the asymmetric catalytic synthesis of chiral propargylamines,and includes the following four chapters:Chapter 1:Introduce and summarize recent progress on the synthesis of propargylamine compounds.Chapter 2:The unprecedented chiral Br?nsted bases-catalyzed asymmetric Mannich reaction of C-alkynyl N-Boc-N,O-acetals and ?-keto esters is demonstrated,effectively affording the syn-propargylamine derivatives bearing two vicinal chiral centers.Meanwhile,the pharmaceutically important ?-alkynyl ?-amino acids and their derivatives also have been synthesized.Chapter 3:Chiral phosphoric acid-catalyzed asymmetric Friedel-Crafts arylation of C-alkynyl N-Boc-N,O-acetals and phenols is demonstrated.The reaction afforded the enantioenriched arylated propargylamines by employing phenols as the nucleophilic arylating reagent.Moreover,the electron-deficient phenols have firstly been employed as an excellent nucleophilic reagent in the asymmetric Friedel-Craft alkylation reaction.Additionally,the Friedel-Crafts alkylated products have been demonstrated to conduct the controlled partial reduction of the alkynyl groups and sequential cross-couplings of the substituted aryl group.Chapter 4:Chiral lithium phosphate-catalyzed asymmetric N-propargylation reaction of carbazoles and indoles with C-alkynyl N-Boc-N,O-acetals is introduced.Notably,owing to the excellent catalytic efficiency,the amount of the SPINOL lithium phosphates could be decreased to 0.1 mol%,and the reaction still proceeded smoothly with the uniform results.This strategy not only referred to the achievement of the asymmetric N-propargylation reaction of carbazoles and indoles,but also developed a straightforward and efficient catalytic enantioselective protocol to construct chiral functionalized N,N-acetals.