The title compound was synthesized by the reaction of adipyl chloride with cyclohexanone piperidine enamine and its structure was finally confirmed by the single - crystal determination in addition to conventional IR,...The title compound was synthesized by the reaction of adipyl chloride with cyclohexanone piperidine enamine and its structure was finally confirmed by the single - crystal determination in addition to conventional IR, (HNMR)-H-1 and elemental analysis.展开更多
Diels-Alder reaction is one of the most important reactions in organic synthesis and has witnessed great achievements in total syntheses of complex natural products.In this review,we will focus on the [4+2] cycloaddit...Diels-Alder reaction is one of the most important reactions in organic synthesis and has witnessed great achievements in total syntheses of complex natural products.In this review,we will focus on the [4+2] cycloaddition that utilizes 2-pyrone as the diene component.Major advances of its applications in the total syntheses of natural products in the past fifty years will be discussed here.展开更多
Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,N...Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.展开更多
An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out unde...An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out under transition-metal-free conditions.A broad range of functional groups were tolerant under mild conditions,and a variety of 2-pyrones were obtained in moderate to good yields.展开更多
A facile method for transesterification was reported. Under catalysis by samarium tri-2-propoxide the yields of transesterification are good to excellent, and this reaction has surprising selectivity and mildness due ...A facile method for transesterification was reported. Under catalysis by samarium tri-2-propoxide the yields of transesterification are good to excellent, and this reaction has surprising selectivity and mildness due to the neutral condition during the reaction.展开更多
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
In this study, the tribological behavior of an ammonium-based protic ionic liquid(PIL) as an additive in a base mineral oil(MO) is investigated on a steel–steel contact at room temperature and 100℃. Tri-[bis(2-hydro...In this study, the tribological behavior of an ammonium-based protic ionic liquid(PIL) as an additive in a base mineral oil(MO) is investigated on a steel–steel contact at room temperature and 100℃. Tri-[bis(2-hydroxyethylammonium)] citrate(DCi) was synthesized in a simple and low-cost way, and the ionic structure of DCi was confirmed by proton nuclear magnetic resonance(^(1)H NMR). The stability measurement of 1 wt% DCi to a MO was investigated, and the lubricating ability and anti-wear properties of DCi as an additive in MO were also examined using a custom-designed reciprocating ball-on-flat tribometer. Optical microscope and profilometry were used to obtain the worn morphology of the steel disks. Scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS) were carried out to investigate the wear mechanism and to analyze the surface interactions between the rubbing components. When 1 wt% DCi is added into the base MO, frictional performance is improved at both temperatures studied with a friction reduction of 29.0% and 35.5%, respectively. Moreover, the addition of 1 wt% DCi to MO reduced the wear volume 59.4% compared to the use of MO. An oxygen-richened tribolayer is confirmed by EDS on the disk surface when DCi was used as additive under 100℃.展开更多
文摘The title compound was synthesized by the reaction of adipyl chloride with cyclohexanone piperidine enamine and its structure was finally confirmed by the single - crystal determination in addition to conventional IR, (HNMR)-H-1 and elemental analysis.
基金The National Natural Science Foundation of China (Grant No. 21801043), the "Z1000-Youth Talents Plan", and Fudan University (start-up gra nt) are ack no wledged for fi nan cial support.
文摘Diels-Alder reaction is one of the most important reactions in organic synthesis and has witnessed great achievements in total syntheses of complex natural products.In this review,we will focus on the [4+2] cycloaddition that utilizes 2-pyrone as the diene component.Major advances of its applications in the total syntheses of natural products in the past fifty years will be discussed here.
基金supported by the National Key R&D Program of China (2017YFA0204704)the National Natural Science Foundation of China (21602105)+2 种基金the General Program of Chongqing Natural Science(cstc2020jcyj-msxmX0712)Ningbo Natural Science Foundation (202003N4063)the Natural Science Foundation of Jiangsu Province (BK20221309)
文摘Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.
基金This work was supported by the National Natural Science Foundation of China(Nos.81573286 and 81373259).
文摘An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out under transition-metal-free conditions.A broad range of functional groups were tolerant under mild conditions,and a variety of 2-pyrones were obtained in moderate to good yields.
文摘A facile method for transesterification was reported. Under catalysis by samarium tri-2-propoxide the yields of transesterification are good to excellent, and this reaction has surprising selectivity and mildness due to the neutral condition during the reaction.
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.
文摘In this study, the tribological behavior of an ammonium-based protic ionic liquid(PIL) as an additive in a base mineral oil(MO) is investigated on a steel–steel contact at room temperature and 100℃. Tri-[bis(2-hydroxyethylammonium)] citrate(DCi) was synthesized in a simple and low-cost way, and the ionic structure of DCi was confirmed by proton nuclear magnetic resonance(^(1)H NMR). The stability measurement of 1 wt% DCi to a MO was investigated, and the lubricating ability and anti-wear properties of DCi as an additive in MO were also examined using a custom-designed reciprocating ball-on-flat tribometer. Optical microscope and profilometry were used to obtain the worn morphology of the steel disks. Scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS) were carried out to investigate the wear mechanism and to analyze the surface interactions between the rubbing components. When 1 wt% DCi is added into the base MO, frictional performance is improved at both temperatures studied with a friction reduction of 29.0% and 35.5%, respectively. Moreover, the addition of 1 wt% DCi to MO reduced the wear volume 59.4% compared to the use of MO. An oxygen-richened tribolayer is confirmed by EDS on the disk surface when DCi was used as additive under 100℃.