The stereoselective synthesis of the C1-C7 fragment (3R,4S,6R)-3,4-di[(tert-butyl-dimethylsilyl)oxy]-7-hydroxy-6-methylheptan-2-one, which is the crucial intermediate for synthesis of the HIV-1 protease inhibitive did...The stereoselective synthesis of the C1-C7 fragment (3R,4S,6R)-3,4-di[(tert-butyl-dimethylsilyl)oxy]-7-hydroxy-6-methylheptan-2-one, which is the crucial intermediate for synthesis of the HIV-1 protease inhibitive didemnaketals, was developed via 12 steps from the natural (+)-pulegone.展开更多
A highly efficient and practical synthesis for strained special scaffold of chiral endo-biarylnorbornane starting from available norbornadione was achieved with direct stereoselective dehydroxylation of tertiary alcoh...A highly efficient and practical synthesis for strained special scaffold of chiral endo-biarylnorbornane starting from available norbornadione was achieved with direct stereoselective dehydroxylation of tertiary alcohol as the key step,and the structure was illustrated by X-ray structural analysis.展开更多
Atropisomeric C-N compounds belong to an important class of axially chiral compounds.However,whereas the asymmetric synthesis of biaryl atropisomers have been well established,general and efficient strategies to acces...Atropisomeric C-N compounds belong to an important class of axially chiral compounds.However,whereas the asymmetric synthesis of biaryl atropisomers have been well established,general and efficient strategies to access single enantiomers of C-N atropisomers are still rare.Until recently,innovative methods have been developed,providing new opportunities for the highly stereoselective synthesis of this vital class of atropisomers.Herein,we comprehensively summarize the development in this emerging field and give some insights into future advance.Emphasis is placed on the synthetic strategies.展开更多
Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved...Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.展开更多
文摘The stereoselective synthesis of the C1-C7 fragment (3R,4S,6R)-3,4-di[(tert-butyl-dimethylsilyl)oxy]-7-hydroxy-6-methylheptan-2-one, which is the crucial intermediate for synthesis of the HIV-1 protease inhibitive didemnaketals, was developed via 12 steps from the natural (+)-pulegone.
基金National Natural Science Foundation of China(Nos.30971934,31272074).
文摘A highly efficient and practical synthesis for strained special scaffold of chiral endo-biarylnorbornane starting from available norbornadione was achieved with direct stereoselective dehydroxylation of tertiary alcohol as the key step,and the structure was illustrated by X-ray structural analysis.
基金Financial support from the National Natural Science Foundation of China(Nos.21925109 and 21772170)the Open Research Fund of School Chemistry and Chemical Engineering,Henan Normal University and the Center of Chemistry for Frontier Technologies of Zhejiang University is gratefully acknowledged.
文摘Atropisomeric C-N compounds belong to an important class of axially chiral compounds.However,whereas the asymmetric synthesis of biaryl atropisomers have been well established,general and efficient strategies to access single enantiomers of C-N atropisomers are still rare.Until recently,innovative methods have been developed,providing new opportunities for the highly stereoselective synthesis of this vital class of atropisomers.Herein,we comprehensively summarize the development in this emerging field and give some insights into future advance.Emphasis is placed on the synthetic strategies.
基金the National Science Foundation of China(grant nos.22031003 and 21720102004)the Shanghai Science Technology Committee,China(grant no.19DZ2270100)the Shanghai Post-doctoral Excellence Program,China(grant no.2022009).
文摘Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.
