The packed density, detonation velocities, and detonation pressures of a series of cyclopropane derivatives were investigated to look for high energy density compounds. For exploring the possibility of synthesis, the ...The packed density, detonation velocities, and detonation pressures of a series of cyclopropane derivatives were investigated to look for high energy density compounds. For exploring the possibility of synthesis, the bond order, heats of formation(HOF), bond dissociation energy(BDE), and characteristic height were calculated. Based on our results, A3 has the best detonation characters. Both A1 and A2 showed comparative detonation parameters and compact sensitivity with RDX, and could be regarded as the candidates of high energy density molecules.Both the heats of formation and explosive heats rose with the increase of nitrimino groups and the strain energy of three-membered ring. For A1 compound, pyrolysis mechanism might be a mix one(breakages of C–C and N–NO2 bonds). However, for A2 and A3 compounds, the N–NO2 is the trigger bond in explosive reactions. Our results may provide the basic information for further study of this kind of compounds.展开更多
Eight pairs of enantiomers of cyclopropane derivatives were resolved on capillary gas chromatographic columns using three new 2, 6-di-O-allyl-3-O-acylated-β-cyclodextrins as chiral stationary phases. It was found th...Eight pairs of enantiomers of cyclopropane derivatives were resolved on capillary gas chromatographic columns using three new 2, 6-di-O-allyl-3-O-acylated-β-cyclodextrins as chiral stationary phases. It was found that the three β-CDs can separate some of the racemic cyclopropane derivatives well.展开更多
In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleop...The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.展开更多
Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem as...Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.展开更多
The fluorine-containing trans-l,2-cyclopropane derivatives 4ba--4dd were synthesized from the fluorine-containing electron-deficient alkenes 3a--3d with semistabilized arsonium ylides 2b--2d, in biphasic system of dic...The fluorine-containing trans-l,2-cyclopropane derivatives 4ba--4dd were synthesized from the fluorine-containing electron-deficient alkenes 3a--3d with semistabilized arsonium ylides 2b--2d, in biphasic system of dichloromethane-50% aqueous sodium hydroxide, generated in situ from the corresponding arsonium salts 1b-1d at room temperature in good yields with high stereoselectivity. The structure of fluorine-containing trans-1,2-cyclopropane derivatives were also studied.展开更多
In the presence of KF·2H2O, furoylmethyltriphenylarsonium bromide （1a） or thienoylmethyltriphenylarsonium bromide （1b） reacted with 2-[（un）substituted benzylidene]malononitrile （2） in chloroform at room t...In the presence of KF·2H2O, furoylmethyltriphenylarsonium bromide （1a） or thienoylmethyltriphenylarsonium bromide （1b） reacted with 2-[（un）substituted benzylidene]malononitrile （2） in chloroform at room temperature to give trans-3,3-dicyano-1-furoyl-2-[（un）substituted phenyl]cyclopropane （3a） or trans-3,3-dicyano-1-thienoyl-2- [（un）substituted phenyl]cyclopropane （3b） respectively in good yield with high stereoselectivity. The structures of product 3 were confirmed by IR, MS, 1^H NMR, 1^H-1^H COSY and microanalysis. The relative configuration of product 3 was determined by 1^H-1^H NOESY technique. The mechanism for the formation of product 3 was also proposed.展开更多
A new chemical transformation for the construction of diversely functionalized cyclopropane-phosphorus derivatives utilizing chiron 4 and racemic diethyl α-hydroxylbenzylphosphonate as the key precursors is described...A new chemical transformation for the construction of diversely functionalized cyclopropane-phosphorus derivatives utilizing chiron 4 and racemic diethyl α-hydroxylbenzylphosphonate as the key precursors is described. The diastereomeric pure phosphorus-containing derivatives 5a, 5′a, 5b and 5′b were obtained respectively, in good yields with d. e. 98% via asymmetric tandem double Michael addition/internal nucleophilic substitution of the corresponding compounds and further through the separation of the diastereomeric mixture by column chromatography. The diversely functionalized phosphorus derivatives are identified on the basis of their elemental analysis and spectroscopic data, such as K, 1H NMR, 13C NMR and MS. The absolute configuration of the interesting cyclopropane-phosphorus compound 5a was established by X-ray crystallography. Thus, these results provide a valuable strategy for synthesizing some biologically active molecules.展开更多
Phorbol esters are recognized for their dual role as anti-HIV-1 agents and as activators of protein kinase C(PKC).The efficacy of phorbol esters in binding with PKC is attributed to the presence of oxygen groups at po...Phorbol esters are recognized for their dual role as anti-HIV-1 agents and as activators of protein kinase C(PKC).The efficacy of phorbol esters in binding with PKC is attributed to the presence of oxygen groups at positions C20,C3/C4,and C9 of phorbol.Concurrently,the lipids located at positions C12/C13 are essential for both the anti-HIV-1 activity and the formation of the PKC-ligand complex.The influence of the cyclopropane ring at positions C13 and C14 in phorbol derivatives on their anti-HIV-1 activity requires further exploration.This research entailed the hydrolysis of phorbol,producing seco-cyclic phorbol derivatives.The anti-HIV-1 efficacy of these derivatives was assessed,and the affinity constant(Kd)for PKC-δprotein of selected seco-cyclic phorbol derivatives was determined through isothermal titration calorimetry.The findings suggest that the chemical modification of cyclopropanols could affect both the anti-HIV-1 activity and the PKC binding affinity.Remarkably,compound S11,with an EC_(50) of 0.27μmol·L^(−1) and a CC_(50) of 153.92μmol·L^(−1),demonstrated a potent inhibitory effect on the intermediate products of HIV-1 reverse transcription(ssDNA and 2LTR),likely acting at the viral entry stage,yet showed no affinity for the PKC-δprotein.These results position compound S11 as a potential candidate for further preclinical investigation and for studies aimed at elucidating the pharmacological mechanism underlying its anti-HIV-1 activity.展开更多
基金supported by the National Natural Science Foundation of China(51374121)
文摘The packed density, detonation velocities, and detonation pressures of a series of cyclopropane derivatives were investigated to look for high energy density compounds. For exploring the possibility of synthesis, the bond order, heats of formation(HOF), bond dissociation energy(BDE), and characteristic height were calculated. Based on our results, A3 has the best detonation characters. Both A1 and A2 showed comparative detonation parameters and compact sensitivity with RDX, and could be regarded as the candidates of high energy density molecules.Both the heats of formation and explosive heats rose with the increase of nitrimino groups and the strain energy of three-membered ring. For A1 compound, pyrolysis mechanism might be a mix one(breakages of C–C and N–NO2 bonds). However, for A2 and A3 compounds, the N–NO2 is the trigger bond in explosive reactions. Our results may provide the basic information for further study of this kind of compounds.
文摘Eight pairs of enantiomers of cyclopropane derivatives were resolved on capillary gas chromatographic columns using three new 2, 6-di-O-allyl-3-O-acylated-β-cyclodextrins as chiral stationary phases. It was found that the three β-CDs can separate some of the racemic cyclopropane derivatives well.
文摘In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
文摘The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29672004)
文摘Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.
基金Project supported by the the National Natural Science Foundation of China （Nos. 20872086 and 20872088）, and the Project of Shanghai Municipal Education Commission （Nos. 09YZ19 and J50102）.
文摘The fluorine-containing trans-l,2-cyclopropane derivatives 4ba--4dd were synthesized from the fluorine-containing electron-deficient alkenes 3a--3d with semistabilized arsonium ylides 2b--2d, in biphasic system of dichloromethane-50% aqueous sodium hydroxide, generated in situ from the corresponding arsonium salts 1b-1d at room temperature in good yields with high stereoselectivity. The structure of fluorine-containing trans-1,2-cyclopropane derivatives were also studied.
基金Project supported by the National Natural Science Foundation of China （No. 20472047）, the Natural Science Foundation of Shanghai （No. 04ZR14060） and the Education Commission of Shanghai Municipality （Nos. 05AX12 and B.99-0303-06-034）.
文摘In the presence of KF·2H2O, furoylmethyltriphenylarsonium bromide （1a） or thienoylmethyltriphenylarsonium bromide （1b） reacted with 2-[（un）substituted benzylidene]malononitrile （2） in chloroform at room temperature to give trans-3,3-dicyano-1-furoyl-2-[（un）substituted phenyl]cyclopropane （3a） or trans-3,3-dicyano-1-thienoyl-2- [（un）substituted phenyl]cyclopropane （3b） respectively in good yield with high stereoselectivity. The structures of product 3 were confirmed by IR, MS, 1^H NMR, 1^H-1^H COSY and microanalysis. The relative configuration of product 3 was determined by 1^H-1^H NOESY technique. The mechanism for the formation of product 3 was also proposed.
文摘A new chemical transformation for the construction of diversely functionalized cyclopropane-phosphorus derivatives utilizing chiron 4 and racemic diethyl α-hydroxylbenzylphosphonate as the key precursors is described. The diastereomeric pure phosphorus-containing derivatives 5a, 5′a, 5b and 5′b were obtained respectively, in good yields with d. e. 98% via asymmetric tandem double Michael addition/internal nucleophilic substitution of the corresponding compounds and further through the separation of the diastereomeric mixture by column chromatography. The diversely functionalized phosphorus derivatives are identified on the basis of their elemental analysis and spectroscopic data, such as K, 1H NMR, 13C NMR and MS. The absolute configuration of the interesting cyclopropane-phosphorus compound 5a was established by X-ray crystallography. Thus, these results provide a valuable strategy for synthesizing some biologically active molecules.
基金supported by the National Natural Science Foundation of China(Nos.81202882 and 82060670)the Suzhou Science and Technology Planning Project in Jiangsu Province of China(No.SNG2021022)+1 种基金the Priority Academic Program Development of the Jiangsu Higher Education Institutes,China(PAPD)Project of Innovative Research Team of Yunnan Province(No.202005AE160005)。
文摘Phorbol esters are recognized for their dual role as anti-HIV-1 agents and as activators of protein kinase C(PKC).The efficacy of phorbol esters in binding with PKC is attributed to the presence of oxygen groups at positions C20,C3/C4,and C9 of phorbol.Concurrently,the lipids located at positions C12/C13 are essential for both the anti-HIV-1 activity and the formation of the PKC-ligand complex.The influence of the cyclopropane ring at positions C13 and C14 in phorbol derivatives on their anti-HIV-1 activity requires further exploration.This research entailed the hydrolysis of phorbol,producing seco-cyclic phorbol derivatives.The anti-HIV-1 efficacy of these derivatives was assessed,and the affinity constant(Kd)for PKC-δprotein of selected seco-cyclic phorbol derivatives was determined through isothermal titration calorimetry.The findings suggest that the chemical modification of cyclopropanols could affect both the anti-HIV-1 activity and the PKC binding affinity.Remarkably,compound S11,with an EC_(50) of 0.27μmol·L^(−1) and a CC_(50) of 153.92μmol·L^(−1),demonstrated a potent inhibitory effect on the intermediate products of HIV-1 reverse transcription(ssDNA and 2LTR),likely acting at the viral entry stage,yet showed no affinity for the PKC-δprotein.These results position compound S11 as a potential candidate for further preclinical investigation and for studies aimed at elucidating the pharmacological mechanism underlying its anti-HIV-1 activity.
