With methyl ester of N-acylated L-3-（3,4-dihydroxyphenyl）alanine（L-DOPA） as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie...With methyl ester of N-acylated L-3-（3,4-dihydroxyphenyl）alanine（L-DOPA） as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski（BN） reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.展开更多
Nitrogen atom doped polycyclic aromatic hydrocarbons,the so-called aza-PAHs,and their conjugated polymers are applicable as functional chromophores and organic semiconductors.Prosperous developments of PAHs and hetero...Nitrogen atom doped polycyclic aromatic hydrocarbons,the so-called aza-PAHs,and their conjugated polymers are applicable as functional chromophores and organic semiconductors.Prosperous developments of PAHs and heterocyclic chemistry have been made possible by considerable improvements in synthetic methodologies,among which one-step reactions leading directly to an aza-conjugated ring are highly desirable.Bischler-Napieralski cyclization,an old yet efficient reaction,can accomplish this task.During the last ten years,this reaction has been successfully used to synthesize a great variety of aza-PAHs molecules.Further combination with polymer chemistry is able to provide the corresponding polymers.This feature article summarizes the up-to-data advances,mainly achieved by our groups,on the design and synthesis of new and well-tailored aza-PAHs and macromolecular architectures using Bischler-Napieralski cyclization as the key step.Furthermore,the versatile applications of these functional materials in the fields of chemosensors,optoelectronic devices,and biomolecular probes are also covered in detail.展开更多
文摘With methyl ester of N-acylated L-3-（3,4-dihydroxyphenyl）alanine（L-DOPA） as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski（BN） reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.
基金Financial support by the National Key Research and Development Program of China(Grants 2017YFA0204503 and 2017YFA0207800)the National Natural Science Foundation of China(Grants 51903187,21734006 and 21975178)the China Postdoctoral Science Foundation(No.2020M670642)is gratefully acknowledged.
文摘Nitrogen atom doped polycyclic aromatic hydrocarbons,the so-called aza-PAHs,and their conjugated polymers are applicable as functional chromophores and organic semiconductors.Prosperous developments of PAHs and heterocyclic chemistry have been made possible by considerable improvements in synthetic methodologies,among which one-step reactions leading directly to an aza-conjugated ring are highly desirable.Bischler-Napieralski cyclization,an old yet efficient reaction,can accomplish this task.During the last ten years,this reaction has been successfully used to synthesize a great variety of aza-PAHs molecules.Further combination with polymer chemistry is able to provide the corresponding polymers.This feature article summarizes the up-to-data advances,mainly achieved by our groups,on the design and synthesis of new and well-tailored aza-PAHs and macromolecular architectures using Bischler-Napieralski cyclization as the key step.Furthermore,the versatile applications of these functional materials in the fields of chemosensors,optoelectronic devices,and biomolecular probes are also covered in detail.
