Polymer Synthesis Through O-H Insertion Of α-diazocarbonyl Compounds With Carboxylic Acids

Diazocarbonyl compounds have played a significant role in modern organic chemistry since various useful organic transformations can be achieved through transition metal-catalyzed reactions.Diazo carbonyl compounds have also been used for the generation of diverse polymers through chain-growth or step-growth polymerizations.O-H insertion of α-diazocarbonyl compounds is a class of unique reactions featuring mild reaction conditions,high efficiency,and good stereoselectivity and regioselectivity.In this dissertation,O-H insertion reactions ofα-diazo carbonyl compounds with carboxylic acids were utilized to synthesize polyesters or poly(ester amide)s.The major findings are as follows:1.Bis(α-diazoacetyleste)compounds with methyl or phenyl substituents were synthesized,and a series of alternative polyesters with various stuctures were prepared through Rh-catalyzed polycondensation of bis(α-diazoacetylesters)compounds with dicarboxylic acids.Thus,we established a mild,efficient,and functional-group-tolerant methodology for polyester synthesis.The number average molecular weights and glass transition temperatures of the resulting polyesters were 6.0-18.4 kg mol-1 and-24-73℃,respectively.This methodology is applicable to polyesters with vinyl,alkynyl,hydroxyl,and amide groups.2.Bis(α-diazoacetylacetamide)compounds with methyl or phenyl substituents were synthesized,and a series of poly(ester amide)s with diverse structures were prepared via Rh-catalyzed polycondensation of bis(α-diazoacetylacetamide)compounds with aliphatic or aromatic dicarboxylic acids.The number average molecular weights and glass transition temperatures of the resulting polyesters were 4.6-17.9 kg mol-1 and 48-226℃,respectively.The versatility of O-H insertion reactions of α-diazo carbonyl compounds with carboxylic acids in step-growth polymerization was further validated in this part.