Asymmetric Catalytic Functional Groups Of Acetylene And Aldehyde Addition Methodology Research

Objective:Optically active propargyl alcohols are important and versatile building blocks for the synthesis of a wide range of pharmace-uticals and natural products.Chiralγ-hydroxy-α,β-acetylenic esters represent a class of functional propargylic alcohols that are very useful and versatile structural subunits in many biologically active compounds.In order to obtain the high selectivity of chiral propargyl alcohol,we used naphthol and amino alcohol system catalyze the acetylene and aldehyde.Methods:Investigate the effects of the type of catalyst,the amount of catalyst,reaction time and the amount of lewis base on the chiral propargyl alcohol’s yield and ee value of the catalysis of acetylene and aldehyde.And select the reaction conditions which can improve yield and ee value of products,the optimized conditions are applied to the different aldehyde.Results:The excellent catalytic effect on methyl propiolate addition to a wide range of aromatic and aliphatic aldehydes promoted by inexpensive and commercially available（R）-6,6’-dibromo-1,1’-bi-2-naphthol ligand is reported.The catalyst systems showed high yields and excellent enantioselectivities for aromatic aldehydes,and excellent yields and high enantioselectivities for aliphatic aldehydes.Asymmetric catalysis of buta-1,3-diyn-1-yltriiso-propyl-silane with aldehyde by chiral amino alcohol ligand-Zn（OTf）₂-Et₃N system was studied,the yield of benaldehyde was 59%,ee value was 95%,however the yield and ee of cycohexyl foraldehyde and isobuty aldehyde were all 95%.Conclusion:The catalytic reaction system of methyl propionate and aldehydes is established,and the products can achieve high yield and ee value.At the same time,the optimum conditions for the reaction of terminal diacetylenes and aldehydes are also initially established,in which theα-branched aldehydes have a good reaction effect.