An improved strategy for the synthesis of 3,3＇-（oxy-p-phenylene）bis（2,4,5-triphenylcyclopentadienone） was developed, which includes three steps： Friedel-Crafts reaction, oxidation and condensation. Importantly, ...An improved strategy for the synthesis of 3,3＇-（oxy-p-phenylene）bis（2,4,5-triphenylcyclopentadienone） was developed, which includes three steps： Friedel-Crafts reaction, oxidation and condensation. Importantly, the use of KMnO4 made the second step simple and efficient, which has potential application to synthesis of bis（cyclopentadienone）s. The course of oxidation has been confirmed by isolated intermediates.展开更多
The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate ...The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate in pyridine was used to effect intramolecular oxidative coupling of 6 under high dilution conditions. During the course of this work a few Diels-Alder reactions of cyclopentadienone 6 were also examined.展开更多
The photolysis results of new diferrocenyl substituted cyclopentadienone（3） show that sunlight and air play an important role in the decomposition of compound 3, and two new compounds, 2-cyclopentenone（4） and a-py...The photolysis results of new diferrocenyl substituted cyclopentadienone（3） show that sunlight and air play an important role in the decomposition of compound 3, and two new compounds, 2-cyclopentenone（4） and a-pyrone（5）, were obtained via photolysis of compound 3. The photolysis process was investigated by IH NMR, and a plausible mechanism for the formation of compound 5 was deduced. The cycloaddition reactions of substituted cyclopentadienones（3, 7, 9） with maleimide gave substituted imides 8, 10, 11, 12 and an unprecedented diferrocenyl substituted 1H-pyrrol-3（2H）-one derivative 13, respectively. The structures of compounds 4, 5, 8, 10, 11, 12 and 13 were confirmed by X-ray single crystal diffraction analysis technique.展开更多
Dimeric sesquiterpenoids possessing densely substituted 7-norbornenone/7-norbornenol motifs pose a considerable challenge for chemical synthesis. From a strategic perspective, one could envision intermolecular Diels-A...Dimeric sesquiterpenoids possessing densely substituted 7-norbornenone/7-norbornenol motifs pose a considerable challenge for chemical synthesis. From a strategic perspective, one could envision intermolecular Diels-Alder cycloaddition as a straightforward method for assembling alkyl-substituted 7-norbornenones. However, this approach is hindered by lability of the required dienes, namely alkylsubstituted cyclopentadienones. Here we report a one-pot protocol for construction of alkyl-substituted7-norbornenones from electron-deficient olefins and a cyclopentenone derivative. DDQ was found to be an effective oxidant for generating a cyclopentadienone intermediate in situ from the enone. A series of sterically congested 7-norbornenone-containing polycyclic compounds were prepared by using this protocol.展开更多
The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster wit...The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.展开更多
基金the National Natural Science Foundation of China for financial support(Nos.5087309350903075)
文摘An improved strategy for the synthesis of 3,3＇-（oxy-p-phenylene）bis（2,4,5-triphenylcyclopentadienone） was developed, which includes three steps： Friedel-Crafts reaction, oxidation and condensation. Importantly, the use of KMnO4 made the second step simple and efficient, which has potential application to synthesis of bis（cyclopentadienone）s. The course of oxidation has been confirmed by isolated intermediates.
文摘The diester diacetylene macrocyclic cyclopentadienone 8 was prepared from the open chain diester acetylene cyclopentadienone 6 in high yield, using the classical Eglinton-Galbraith procedure [1]. Copper（lI） acetate in pyridine was used to effect intramolecular oxidative coupling of 6 under high dilution conditions. During the course of this work a few Diels-Alder reactions of cyclopentadienone 6 were also examined.
基金Supported by the National Natural Science Foundation of China（Nos.21266019, 21062011）.
文摘The photolysis results of new diferrocenyl substituted cyclopentadienone（3） show that sunlight and air play an important role in the decomposition of compound 3, and two new compounds, 2-cyclopentenone（4） and a-pyrone（5）, were obtained via photolysis of compound 3. The photolysis process was investigated by IH NMR, and a plausible mechanism for the formation of compound 5 was deduced. The cycloaddition reactions of substituted cyclopentadienones（3, 7, 9） with maleimide gave substituted imides 8, 10, 11, 12 and an unprecedented diferrocenyl substituted 1H-pyrrol-3（2H）-one derivative 13, respectively. The structures of compounds 4, 5, 8, 10, 11, 12 and 13 were confirmed by X-ray single crystal diffraction analysis technique.
基金supported by Ministry of Science and Technology (National Key Research and Development Program of China,Nos. 2019YFC1711000 and 2018YFA0901900)National Natural Science Foundation of China (Nos. 21931014, 21525209, 21621002,21772225, 21761142003 and 82003624)+5 种基金Chinese Academy of Sciences (Strategic Priority Research Program, No. XDB20000000International Partner Program, No. 121731KYSB20190039Key Research Program of Frontier Sciences, No. QYZDB-SSW-SLH040)Science and Technology Commission of Shanghai Municipality (Nos.17XD1404600 and 20YF1458700)State Key Laboratory of Innovative Natural Medicine and Traditional Chinese Medicine Injections(No. QFSKL2017002)K.C. Wong Education Foundation。
文摘Dimeric sesquiterpenoids possessing densely substituted 7-norbornenone/7-norbornenol motifs pose a considerable challenge for chemical synthesis. From a strategic perspective, one could envision intermolecular Diels-Alder cycloaddition as a straightforward method for assembling alkyl-substituted 7-norbornenones. However, this approach is hindered by lability of the required dienes, namely alkylsubstituted cyclopentadienones. Here we report a one-pot protocol for construction of alkyl-substituted7-norbornenones from electron-deficient olefins and a cyclopentenone derivative. DDQ was found to be an effective oxidant for generating a cyclopentadienone intermediate in situ from the enone. A series of sterically congested 7-norbornenone-containing polycyclic compounds were prepared by using this protocol.
基金supported by the National Natural Science Foundation of China(Nos.21266019,21062011 and 21462029)Inner Mongolia Autonomous Region Higher Scientific Research Project(NJZY14060)
文摘The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
