Chiral heteroatom-containing bicyclic scaffolds are important pharmacophores and prevalent in bioactive natural products and drug molecules.Herein,we report a unified approach for the divergent synthesis of chiral het...Chiral heteroatom-containing bicyclic scaffolds are important pharmacophores and prevalent in bioactive natural products and drug molecules.Herein,we report a unified approach for the divergent synthesis of chiral heteroatom-containing bicyclic derivatives by lanthanide(lil)-catalyzed asymmetric inverse-electron-demand Diels-Alder reactions of 2-pyrones.These reactions occur with vari-ous readily available dihydropyrroles and dihydrofurans as dienophiles,providing a step-economical synthetic platform for densely functionalized ciss-hydroindoles and cis-hydrobenzofurans with excellent yields and enantioselectivities.The synthetic utility of this approach is demonstrated by the concise synthesis of(-)-α-lycorane and(-)-lycorine alkaloids.展开更多
Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However...Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.展开更多
This research paper describes the synthesis of thermo-reversible cross-linking of sago starch by grafting a furan pendant group(methyl 2-furoate)onto the starch backbone,followed by a Diels-Alder(DA)reaction of the fu...This research paper describes the synthesis of thermo-reversible cross-linking of sago starch by grafting a furan pendant group(methyl 2-furoate)onto the starch backbone,followed by a Diels-Alder(DA)reaction of the furan functional group with 1,1′-(methylenedi-4,1-phenylene)bismaleimide(BM).The proof of principles was provided by FTIR and 1H-NMR analyses.The relevant FTIR peaks are the carbonyl peak(υC=O sym)at 1721 cm^(−1);the two peaks appeared after DA cross-linking,i.e.,at 1510 cm^(−1)(corresponding toυCH=CH BM aromatic rings,stretching vibrations),and at 1173 cm^(−1)(assigned to cycloadduct(C-O-C,δDA ring))while the^(1)H-NMR result shows evidence for the presence of a furan ring in the starch matrices(in the range ofδ6.3-7.5 ppm).The crosslinked starch product is indeed thermally reversible,as is evident from the appearance of exothermal(DA,temperature range of 50℃-70℃)and endothermal(retro DA,temperature range of 125℃-150℃)transitions in the DSC thermograms.This paper not only proves the thermal reversibility but also demonstrates that the final product properties(chemical,morphology,and thermal stability)can be tuned by varying the annealing temperature,BM intake,and reaction time.展开更多
基金the National Natural Science Foundation of China(Grant No.22071030)Fudan University for financial support。
文摘Chiral heteroatom-containing bicyclic scaffolds are important pharmacophores and prevalent in bioactive natural products and drug molecules.Herein,we report a unified approach for the divergent synthesis of chiral heteroatom-containing bicyclic derivatives by lanthanide(lil)-catalyzed asymmetric inverse-electron-demand Diels-Alder reactions of 2-pyrones.These reactions occur with vari-ous readily available dihydropyrroles and dihydrofurans as dienophiles,providing a step-economical synthetic platform for densely functionalized ciss-hydroindoles and cis-hydrobenzofurans with excellent yields and enantioselectivities.The synthetic utility of this approach is demonstrated by the concise synthesis of(-)-α-lycorane and(-)-lycorine alkaloids.
基金supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.
基金funded by the Indonesia Toray Science Foundation(No.:001/I/ITSF/SEK/2019).
文摘This research paper describes the synthesis of thermo-reversible cross-linking of sago starch by grafting a furan pendant group(methyl 2-furoate)onto the starch backbone,followed by a Diels-Alder(DA)reaction of the furan functional group with 1,1′-(methylenedi-4,1-phenylene)bismaleimide(BM).The proof of principles was provided by FTIR and 1H-NMR analyses.The relevant FTIR peaks are the carbonyl peak(υC=O sym)at 1721 cm^(−1);the two peaks appeared after DA cross-linking,i.e.,at 1510 cm^(−1)(corresponding toυCH=CH BM aromatic rings,stretching vibrations),and at 1173 cm^(−1)(assigned to cycloadduct(C-O-C,δDA ring))while the^(1)H-NMR result shows evidence for the presence of a furan ring in the starch matrices(in the range ofδ6.3-7.5 ppm).The crosslinked starch product is indeed thermally reversible,as is evident from the appearance of exothermal(DA,temperature range of 50℃-70℃)and endothermal(retro DA,temperature range of 125℃-150℃)transitions in the DSC thermograms.This paper not only proves the thermal reversibility but also demonstrates that the final product properties(chemical,morphology,and thermal stability)can be tuned by varying the annealing temperature,BM intake,and reaction time.
