Xiang-Kai FU

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Name: 傅相锴

Organization: College of Chemistry and Chemical Engineering Southwest University , China

Department: Research Institute of Applied Chemistry Southwest University

Title: NULL(PhD)

TOPICS

Inorganic Chemistry

Organic Chemistry

Trifluoromethylation

Chemicals
References

Synthesis and characterization of novel electrochromic and photoresponsive materials based on azobenzene-4,4′-dicarboxylic acid dialkyl ester

Co-reporter:Li-hua He, Guo-ming Wang, Qian Tang, Xiang-kai Fu and Cheng-bin Gong

Journal of Materials Chemistry A 2014 vol. 2(Issue 38) pp:8162-8169

Publication Date(Web):06 Aug 2014

DOI:10.1039/C4TC01205D

Novel electrochromic and photoresponsive materials based on azobenzene-4,4′-dicarboxylic acid dialkyl ester derivatives (ADDEDs) were successfully prepared and characterized through nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and high-performance liquid chromatography-mass spectrometry. The electrochromic behavior, electrochromic mechanism, electro-optical properties, and photoresponsive properties of ADDEDs were investigated through cyclic voltammetry and ultraviolet-visible absorption spectra. ADDEDs displayed not only outstanding electrochromic behavior but also good and reversible photoisomerization properties even under electrochromic conditions. Electrochromic devices (ECDs) based on ADDEDs were fabricated, and their electrochromic performance was analyzed. The ECDs presented a color change from colorless to magenta between 0.0 V (bleached state) and ±3.0 V (colored state). In addition, the ECDs exhibited fast switching times, reasonable contrast, satisfactory optical memories, and redox stability. The novel redox-active azobenzene derivatives are promising candidates for full-color EC display devices, electronic paper, smart windows, optical memory devices, dual-stimuli-responsive systems, as well as other potential new applications.

Synthesis, electrochemical and electrochromic properties of novel 2,4,6-Tri(pyridine-4-yl)pyridilium derivatives

Co-reporter:Guoming Wang, Xiangkai Fu, Lihua He, Xuemei Huang, Qiang Miao

Organic Electronics 2014 Volume 15(Issue 2) pp:622-630

Publication Date(Web):February 2014

DOI:10.1016/j.orgel.2013.12.015

•New electrochromic materials 2,4,6-Tri(pyridine-4-yl)pyridilium derivatives (TPPDs) were synthesized.•Electrochromic devices based on four TPPDs were assembled for the first time.•The mechanism of the electrochromism and electrochemistry of the ECDs was proposed and discussed.•The ECD exhibited a fast switching time, superior cycling stability and well electrochromic behavior.Four star-shaped like fused heterocyclic compounds multi-electrochromic materials 2,4,6-Tri(pyridine-4-yl)pyridilium derivatives (TPPDs) were successfully synthesized and characterized by NMR, Solid IR spectra, APCI-MS, and UV–vis spectroscopy. The electrochemical properties, electrochromic behavior, electro-optical properties, and electrochromic mechanism were investigated by thermogravimetric analysis, cyclic voltammetry and UV–vis absorption spectra. Electrochromic devices based on these compounds were fabricated with an active area of 3 cm × 4 cm and their electrochromic performances were further studied. It was found the ECDs presented a stable as well as multicolor electrochromic change from colorless to blue, then violet-blue and finally black-blue between 0 V and +4.0 V. In addition, the prepared electrochromic materials had high coloration efficiency, low switching time, and nice redox stability. This type of multi-electrochromic materials would thus be promising candidates for applications in electrochromic devices.Graphical abstract

Synthesis, electrochemical and electrochromic properties of novel pyridinium salts based on 2,6-di(4-pyridyl)-4-benzylpyridilium

Co-reporter:Guoming Wang, Xiangkai Fu, Lihua He, Qiang Miao, Guilong Peng

Chemical Physics Letters 2014 Volume 614() pp:243-250

Publication Date(Web):20 October 2014

DOI:10.1016/j.cplett.2014.08.040

Highlights

•: New electrochromic materials 2,6-di(4-pyridyl)-4-benzylpyridilium derivatives (DPBPDs) were synthesized.
•: Electrochromic devices based on four DPBPDs were assembled for the first time.
•: The mechanism of the electrochromism and electrochemistry of the ECDs was proposed and discussed.
•: The ECD exhibited a fast switching time, superior cycling stability and well electrochromic behavior.

Chiral salen Mn(III) complexes immobilized onto crystalline aluminium oligo-styrenyl phosphonate-hydrogen phosphate (AlSPP) for heterogeneous asymmetric epoxidation

Co-reporter:Xuemei Huang, Xiangkai Fu, Ziyong Jia, Qiang Miao and Guoming Wang

Catalysis Science & Technology 2013 vol. 3(Issue 2) pp:415-424

Publication Date(Web):14 Sep 2012

DOI:10.1039/C2CY20394D

A novel type of organic polymer–inorganic hybrid material layered crystalline aluminium oligo-styrenyl phosphonate-hydrogen phosphate (AlSPP) was designed and prepared in the absence of any template. The chiral salen Mn(III) complex immobilized onto alkoxy-modified AlSPP was synthesized and characterized by FT-IR, diffusion reflection UV-vis, AAS, N2 volumetric adsorption, SEM, TEM, XRD, TG and AFM. The supported catalysts displayed superior catalytic activities in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA as an oxidant. Delightfully, the heterogeneous catalysts afforded a remarkable increase in conversion and ee values without the expensive O-coordinating axial bases for the asymmetric epoxidation of olefins. The catalysts can be easily recovered and reused with a slight decrease in activity and enantioselectivity after ten cycles. Furthermore, they could also be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which provided the potentiality for application in industry.

Electrochromic and spectroelectrochemical properties of novel 4,4′-bipyridilium–TCNQ anion radical complexes

Co-reporter:Guoming Wang, Xiangkai Fu, Jun Deng, Xuemei Huang, Qiang Miao

Chemical Physics Letters 2013 Volume 579() pp:105-110

Publication Date(Web):30 July 2013

DOI:10.1016/j.cplett.2013.06.037

•New electrochromic materials monosubstituted 4,4′-bipyridilium–TCNQ anion radical salts (MBTS) were synthesized.•Electrochromic devices based on MBTS were assembled for the first time.•The mechanism of the electrochromism and electrochemistry of the ECD was proposed and discussed.•The ECD exhibited a fast switching time, superior cycling stability and well electrochromic behavior.Three novel electrochromic materials 7,7,8,8-tetracyanoquinodimethane (TCNQ) anion radical salts with substituted 4,4′-bipyridilium derivatives (monosubstituent-4,4′-bipyridilium) were prepared. The structure of the complexes was characterized by Elemental analyses, Solid IR spectra and UV–vis spectroscopy. The electrochromic behaviors and electrooptical properties of the complexes were investigated by cyclic voltammetry and UV–vis absorption spectra. Electrochromic devices based on monosubstituent 4,4′-bipyridilium–TCNQ anion radical salts (abbreviated as MBTS) were fabricated which exhibited green–magenta color change. Their color reversibility was excellent with high color-change efficiency after 1000 cycles of the transmittance and transmittance change.

Novel bis-Salen Mn(III) chiral complexes of rigid structure axially coordinated with bis-diphenolate and bis-diamine for epoxidation of unfunctionalized olefins

Co-reporter:Xuemei Huang, Xiangkai Fu, Xiaoju Wu, Ziyong Jia

Tetrahedron Letters 2013 Volume 54(Issue 31) pp:4041-4044

Publication Date(Web):31 July 2013

DOI:10.1016/j.tetlet.2013.05.087

A series of bis-Salen Mn(III) chiral complexes of rigid structure axially coordinated with bis-diphenolate and bis-diamine ligands were synthesized and their catalytic performances in asymmetric epoxidation of indene and α-methylstyrene were investigated in detail. Compared with Jacobsen’s catalyst and the corresponding monomer salen Mn(III) catalyst, bis-Salen Mn complex showed higher activity and enantioselectivity under the same reaction conditions. A point worth emphasizing was that the bis-diphenolate axially coordinated bis-Salen Mn catalysts afforded remarkable increases of ee values in the absence of axial base NMO for the asymmetric epoxidation of olefins, especially for the epoxidation of indene (ee: from 55% to 100%), however, the axial base is indispensable for the bis-diamine axially coordinated bis-Salen Mn(III) catalysts, these performance might attribute to the rigid difference of the structure. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it could also be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which possessed the potentiality for application in industry.A novel type of bis-diphenolate and bis-diamine ligands axially coordinated bis-Salen Mn(III) chiral complexes were synthesized and characterized, their catalytic performances in asymmetric epoxidation of unfunctionalized olefins were investigated in detail.

Enantioselective epoxidation of nonfunctionalized alkenes catalyzed by recyclable new homochiral bis-diamine-bridged bi-Mn(salen) complexes

Co-reporter:XueMei Huang;XiangKai Fu;ZiYong Jia;Qiang Miao;GuoMing Wang

Science China Chemistry 2013 Volume 56( Issue 5) pp:604-611

Publication Date(Web):2013 May

DOI:10.1007/s11426-012-4829-x

Three new homochiral bis-diamine-bridged bi-Mn(salen) complexes were synthesized. Their catalysis on asymmetric epoxidation of α-methylstyrene, styrene and indene was studied with NaClO and m-CPBA as oxidants respectively. This homogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to the Jacobsen’s catalyst in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it also could be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which provided the potential for the applications in industry. The effect of axial bases, temperature and solvent on activity and enantioselectivity of the catalytic system were also studied.

Highly efficient direct large-scale stoichiometric aldol reactions catalyzed by a new diamine salt in the presence of water

Co-reporter:Jing Huang, Guodong Chen, Xiangkai Fu, Chao Li, Chuanlong Wu and Qiang Miao

Catalysis Science & Technology 2012 vol. 2(Issue 3) pp:547-553

Publication Date(Web):05 Dec 2011

DOI:10.1039/C1CY00318F

A new type of primary–tertiary diamine salt prepared can be used as a catalyst for direct aldol reaction and can display high yields, diastereoselectivities (up to 99:1), and enantiomeric excesses (up to 98%), by using stoichiometric amounts of cyclic ketones and various aryl aldehydes in the presence of water. This new catalyst can also be efficiently applied in large-scale reactions with the enantioselectivity being maintained at the same level, which indicates the potential for applications in industry.

The synthesis and electrochemical study of new electrochromic materials vinylbipyridinium derivatives

Co-reporter:Jun Deng, Xiangkai Fu, Gang Wang, Liu Wu, Jing Huang

Electrochimica Acta 2012 Volume 85() pp:195-202

Publication Date(Web):15 December 2012

DOI:10.1016/j.electacta.2012.08.100

In order to develop novel electrochromic materials, four vinylbipyridinium derivatives (VBPDs) were synthesized. The structures of VBPDs were characterized as the vinyl derivatives of viologen by NMR, IR spectroscopy and APCI-MS. The electrochromic behaviors and electro-optical properties of VBPDs were investigated by thermogravimetric analysis, cyclic voltammetry and UV–vis absorption spectra. Moreover, a serial of environmentally friendly electrochromic devices (ECD) based on VBPDs were assembled successfully and their electrochromic performances were further studied. It was found that VBPDs in ECDs showed superior cycling stabilities and well-defined reversibilities, and clear color changes from colorless to magenta/pink during the potential ranges from 0 V (in the oxidized state) to ±1.5 V (in the reduced state). To sum up, the VBPDs synthesized are promising candidates for visible electrochromic devices, for their outstanding electrochromic behaviors plus short and oversimplified synthetic routes.Graphical abstractHighlights► New electrochromic materials VBPDs were synthesized, their structures were characterized as the vinyl derivatives of viologen. ► Electrochromic devices based on new functional materials VBPDs were assembled for the first time. ► The VBPDs present good cycling stabilities and superior electrochromic behaviors.

A series of novel types of immobilized chiral salen Mn(III) on different organic polymer-inorganic hybrid crystalline zinc phosphonate-phosphate act as catalysts for asymmetric epoxidation of unfunctionalized olefins

Co-reporter:Jing Huang, Xiangkai Fu, Gang Wang, Yaqin Ge and Qiang Miao

Catalysis Science & Technology 2012 vol. 2(Issue 5) pp:1040-1050

Publication Date(Web):06 Jan 2012

DOI:10.1039/C2CY00502F

A novel type of layered crystalline organic polymer-inorganic hybrid material, zinc poly(styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPA) was synthesized and an array of new heterogeneous catalysts were gained by grafting chiral salen Mn(III) onto the ZnPS-PVPA, and characterized by FT-IR, diffusion reflection UV-vis, AAS, N2 volumetric adsorption, SEM, TEM, XPS, XRD and TG. The immobilized chiral salen Mn(III) catalysts exhibited higher chiral induction in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA and NaIO4 as oxidants than the corresponding homogeneous catalyst did (ee, >99% vs. 54% and >99% vs. 65%). And the heterogeneous catalysts are relatively stable and can be recycled nine times in the asymmetric epoxidation of α-methylstyrene. Furthermore, this novel type of catalyst can also be efficiently used in large-scale reactions with superior catalytic ability being maintained at the same level, which possessed the potentiality for application in industry.

Chiral salen Mn(III) immobilized onto sulfoalkyl-modified zinc poly(styrene-phenylvinylphosphonate)-phosphate as effective catalysts for epoxidation of unfunctionalized olefins

Co-reporter:Jing Huang, Xiangkai Fu, Changwei Wang, Huaizhi Zhang, Qiang Miao

Microporous and Mesoporous Materials 2012 Volume 153() pp:294-301

Publication Date(Web):1 May 2012

DOI:10.1016/j.micromeso.2011.10.025

The heterogeneous catalysts 3a–3c immobilized chiral salen Mn(III) onto sulfoalkyl-modified zinc poly(styrene-phenylvinylphosphonate)phosphate (ZnPSPPP) were prepared and used for the enantioselective epoxidation of unfunctionalized olefins. The catalysts were characterized with FT-IR, UV–vis, XRD, SEM, TEM. All the prepared heterogeneous catalysts exhibited much higher chiral induction than the homogeneous Jacobsen’s catalyst did and could be reused six times without significant loss of activity and enantioselectivity. Surprisedly, the conversions and enantiomeric excess (ee) values increased in the absence of axial base N-methylmorpholine N-oxide (NMO), which were different to what most literatures reported. Meanwhile, the role of axial ligand NMO in the asymmetric epoxidation of unfunctional olefin was also discussed here. Furthermore, this novel type of catalyst can also be validly used in large-scale reactions with superior catalytic disposition being maintained at the same level, which possessed the potentiality for application in industry.Graphical abstractThe catalysts that sulfoalkyl modified ZnPSPPP were used for the immobilization of chiral salen Mn(III) displayed superior catalytic ability either for the experimental scale reactions or for the large-scale reactions.Highlights► Organic polymer-inorganic hybrid material layered crystalline ZnPSPPP was synthesized and characterized. ► The chiral salen Mn(III) was immobilized on sulfoalkyl modified ZnPSPPP. ► The heterogeneous catalysts displayed superior activity according to the homogeneous catalysts. ► The heterogeneous catalysts could be reused at least 9 times without significant loss of activity. ► The catalysts could be used in large-scale reactions with superior catalytic disposition.

The effect of ionic liquid fragment on the performance of polymer electrolytes

Co-reporter:Qiuliang Du;Xiangkai Fu;Sujuan Liu ;Lidan Niu

Polymer International 2012 Volume 61( Issue 2) pp:222-227

Publication Date(Web):

DOI:10.1002/pi.3172

Abstract

An ionic liquid 1-methyl-3-[2-(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm-TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm-TFSI (PMMEIm-TFSI) and poly[(methyl methacrylate)-co-(vinyl acetate)] (P(MMA-VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm-TFSI up to a maximum value of 1.78 × 10⁻⁴ S cm⁻¹ when the composition was 25 wt% P(MMA-VAc)/75 wt% PMMEIm-TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion-conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry

Synthesis of a layered crystalline AlSPP and reusable catalysts for epoxidation of unfunctionalized olefins

Co-reporter:Ziyong Jia;Xiangkai Fu;Yunfei Luo;Huaizhi Zhang ;Xuemei Huang

Applied Organometallic Chemistry 2012 Volume 26( Issue 6) pp:259-266

Publication Date(Web):

DOI:10.1002/aoc.2842

A type of organic–inorganic hybrid material layered crystalline AlSPP (AlSPP) was prepared under simple conditions, completely different to the traditional hydrothermal methods, by the reaction of oligo-styrenyl phosphonic acid with aluminum acetate and sodium dihydrogen phosphate. The microstructure of AlSPP was characterized by X-ray diffraction, FT-IR, atomic absorption spectroscopy, N₂ volumetric adsorption, atomic force microscopy, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. Based on the experimental date, the ideal structure model of AlSPP is proposed, which indicated that the layered crystalline AlSPP samples are special lamellar structure with many cavums, holes, channels and ravines on the surface, the interlamellar region and interlayer surfaces of the particles. Therefore AlSPP possesses excellent properties and has potential applications for heterogeneous asymmetric catalyst supports. Copyright © 2012 John Wiley & Sons, Ltd.

A high efficient large-scale asymmetric epoxidation of unfunctionalized olefins employing a novel type of chiral salen Mn(III) immobilized onto layered crystalline aryldiamine modified zinc poly(styrene-phenylvinylphosphonate)-phosphate

Co-reporter:Jing Huang, Xiangkai Fu, Gang Wang, Yaqin Ge, Qiang Miao

Journal of Molecular Catalysis A: Chemical 2012 Volume 357() pp:162-173

Publication Date(Web):May 2012

DOI:10.1016/j.molcata.2012.02.008

A series of chiral salen Mn(III) catalysts immobilized onto aryldiamine modified ZnPS-PVPA with different ratio of phosphonate/phosphate for asymmetric epoxidation were synthesized and characterized by FT-IR, diffusion reflection UV–Vis, AAS, N2 volumetric adsorption, SEM, TEM, XPS, XRD and TG. The supported catalysts displayed superior catalytic activities in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA and NaIO4 as oxidants. Moreover, the heterogeneous catalysts were relatively stable and could be recycled nine times in the asymmetric epoxidation of α-methylstyrene. Furthermore, this novel type of catalyst could also be validly used in large-scale reactions with superior catalytic disposition being maintained at the same level, which possessed the potentiality for application in industry.Graphical abstractThe catalysts immobilized salen Mn(III) onto ZnPS-PVPA displayed superior catalytic ability both for experimental scale and for large-scale reactions.Highlights► Organic polymer–inorganic hybrid material layered crystalline ZnPS-PVPA was synthesized and characterized. ► The chiral salen Mn(III) was immobilized on aryldiamine modified ZnPS-PVPA. ► The heterogeneous catalysts displayed superior activity according to the homogeneous catalysts. ► The heterogeneous catalysts could be reused at least nine times without significant loss of activity. ► The catalysts could be used in large-scale reactions with superior catalytic disposition.

Asymmetric epoxidation of unfactionalized olefins catalyzed by chiral salen Mn(III) immobilized onto sulfoalkyl modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate and zirconium poly(styrene-phenylvinyl phosphonate)-phosphate

Co-reporter:Zhijian Liu, Xiangkai Fu, Xiaoyan Hu, Qiang Miao

Journal of Organometallic Chemistry 2012 713() pp: 157-162

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.05.002

Highly efficient direct a larger-scale aldol reactions catalyzed by a flexible prolinamide based-metal Lewis acid bifunctional catalyst in the presence of water

Co-reporter:Guodong Chen, Xiangkai Fu, Chao Li, Chuanlong Wu, Qiang Miao

Journal of Organometallic Chemistry 2012 702() pp: 19-26

Publication Date(Web):

DOI:10.1016/j.jorganchem.2011.12.006

Organocatalysis with cysteine derivatives: recoverable and cheap chiral catalyst for direct aldol reactions

Co-reporter:Shi Li;Xiangkai Fu;Chuanlong Wu

Research on Chemical Intermediates 2012 Volume 38( Issue 1) pp:195-205

Publication Date(Web):2012 January

DOI:10.1007/s11164-011-0336-5

Highly enantioselective, recoverable and cheap cysteine derivatives have been developed with improved solubility properties in common, nonpolar organic solvents. The reactions were catalyzed using 5 mol% 1e, and the aldol products could be obtained with up to 99:1 syn/anti ratio and >99% ee. The catalyst could be easily recovered and reused, with only a slight decrease of enantioselectivity observed for five cycles. Catalyst 1e can be efficiently used in large-scale reactions with enantioselectivity being maintained at the same level, which offers great possibility for application in industry.

Polymer Electrolytes Based on Polymeric Ionic Liquid Poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethane sulfonyl)imide)

Co-reporter:Qiuliang Du;Xiangkai Fu;Sujuan Liu

Journal of Inorganic and Organometallic Polymers and Materials 2012 Volume 22( Issue 2) pp:316-323

Publication Date(Web):2012 March

DOI:10.1007/s10904-011-9636-x

A new kind of ionic liquid monomer methyl 2-(3-vinylimidazolidin-1-yl)acetate bromide (MVIm-Br) and polymeric ionic liquid (PIL), poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethanesulfonyl)imide) (PMVIm-TFSI), were synthesized and characterized. Different compositions of polymer electrolytes were prepared by blending PMVIm-TFSI and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with poly(methylmethacrylate-co-vinyl acetate) (P(MMA-VAc)). The thermal stability and ionic conductivity improved significantly when PMVIm-TFSI was added into P(MMA-VAc)/LiTFSI polymer. For the polymer electrolytes obtained, the highest ionic conductivity at 30 °C is 4.71 × 10−4 S cm−1 and the corresponding decomposition temperature is ca. 308 °C. Moreover, P(MMA-VAc)/PMVIm-TFSI/LiTFSI electrolyte membrane (transmittance ≥90%) can be used as the ion-conductive layer material for electrochromic devices, which reveal excellent electrochromic performance.

Chiral Salen Mn(III) Complex Axial Coordination Immobilized on Diamine Modified Alspp and Highly Efficient Large-Scale Epoxidation of Olefins as a Recoverable Catalyst

Co-reporter:Ziyong Jia;Xiangkai Fu;Yunfei Luo

Journal of Inorganic and Organometallic Polymers and Materials 2012 Volume 22( Issue 2) pp:415-422

Publication Date(Web):2012 March

DOI:10.1007/s10904-011-9571-x

Aluminium oligo-styrenyl phosphonate-hydrogen phosphate (AlSPP) was used as organic–inorganic hybrid support after chloromethylation, and then with using different diamines as a reactive surface modifier. We realized the homogeneous chiral salen Mn(III) complex axially immobilized on modified AlSPP by a covalent grafting method. The prepared heterogeneous salen Mn(III) complexes were characterized by different techniques such as FT-IR, diffusion reflection UV–Vis, AAS, XPS, N2 volumetric adsorption, SEM, TEM and TG. The chiral salen Mn(III) complexes were immobilized onto the AlSPP through axial coordination for the first time with m-CPBA/NMO as an oxidant system for asymmetric epoxidation of unfunctionalized olefins. The supported catalyst showed very good performance in the asymmetric epoxidation of α-methylstyrene and indene. The catalyst could be easily recovered and reused without significant loss of activity and enantioselectivity after nine cycles. This novel heterogeneous catalyst could be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offer great possibilities for application in industry.

Recoverable MnIII(salen) supported on diamine modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Co-reporter:XiaoChuan Zou;ShaoCheng Chen;YanRong Ren;KaiYun Shi;Jun Li

Science China Chemistry 2012 Volume 55( Issue 11) pp:2396-2406

Publication Date(Web):2012/11/01

DOI:10.1007/s11426-012-4600-3

Chiral MnIII(salen) (Jacobsen’s catalyst) was axially immobilized onto a new type of organic polymer-inorganic hybrid material-zirconium poly(styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA) with different linkage lengths and evaluated as catalysts for the epoxidation of unfunctionalized olefins. The results demonstrated that the prepared catalysts exhibited moderate to good activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the immobilized catalysts were relatively stable and could be conveniently separated from the reaction system by simple precipitation in hexane. Moreover, higher enantioselectivity was obtained with catalyst 2c than that of homogeneous counterpart catalyzed even after eight times. The excellent recycling of the catalyst was attributed to its structure feature of ZPS-IPPA which is different from either pure polystyrene or pure zirconium phosphates.

Syntheses and electrochromic and fluorescence properties of three double dithienylpyrroles derivatives

Co-reporter:Gang Wang, Xiangkai Fu, Jing Huang, Chuan Long Wu, Liu Wu, Jun Deng, Qiuliang Du, Xiaochuan Zou

Electrochimica Acta 2011 Volume 56(Issue 18) pp:6352-6360

Publication Date(Web):15 July 2011

DOI:10.1016/j.electacta.2011.05.023

Three double dithienylpyrroles derivatives have been successfully prepared by performing a Knorr–Paal condensation between 1,4-di(thiophen-2-yl) butane-1,4-dione and various aromatic diamines. Additionally, their corresponding polymer films were synthesized via electropolymerization. Their electrochemical, spectroelectrochemical and electrochromic behaviors were further investigated by thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry, UV–vis absorption and fluorescence emission spectra. Scanning electron microscopy and thermogravimetric analysis demonstrated that the polymer films possessed homogeneous, compact and smooth layer structures and thermal stabilities (up to nearly 180 °C). Cyclic voltammograms and UV–vis absorption spectra studies showed that the polymer films have stable, well-defined, reversible redox processes, low optical band gaps (Eg < 2.2 eV) and multicolor electrochromic behaviors. Additionally, the fluorescence spectra study showed that all of the monomers and polymers exhibited different intensity emission bands at different wavelengths.Highlights► Three kinds of double dithienylpyrroles derivatives have been successfully prepared by the Knorr–Paal condensation between 1,4-di(thiophen-2-yl) butane-1,4-dione and aromatic diamines. ► Their polymer films were successfully synthesized via electropolymerization. ► The polymer films had stable and well-defined reversible redox process, low optical band gap and multicolor electrochromic behavior. ► All the monomers and polymers exhibited different intensity emission bands at different wavelengths.

Synthesis of a novel type of chiral salen Mn(III) complex immobilized on crystalline zinc poly(styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPP) as effective catalysts for asymmetric epoxidation of unfunctionalized olefins

Co-reporter:Jing Huang, Xiangkai Fu and Qiang Miao

Catalysis Science & Technology 2011 vol. 1(Issue 8) pp:1472-1482

Publication Date(Web):31 Aug 2011

DOI:10.1039/C1CY00285F

A novel type of organic polymer–inorganic hybrid material layered crystalline ZnPS-PVPP was designed and prepared. Notably, the layered crystalline ZnPS-PVPP were obtained in the absence of any templated agents. An array of new heterogeneous catalysts were gained by grafting chiral salen Mn(III) onto aryldiamine modified ZnPS-PVPP. The immobilized catalysts exhibited higher chiral induction in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA and NaIO4 as oxidants than those of the corresponding homogeneous catalyst (ee, >99% vs. 54% and >99% vs. 65%) and could be reused nine times without significant loss of activity and enantioselectivity. Furthermore, this novel type of catalyst can also be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which provided the potentiality for application in industry.

The synthesis and electrochemical properties of cathodic–anodic composite electrochromic materials

Co-reporter:Xi Tu, Xiangkai Fu, Qinglong Jiang, Zhijian Liu, Guodong Chen

Dyes and Pigments 2011 Volume 88(Issue 1) pp:39-43

Publication Date(Web):January 2011

DOI:10.1016/j.dyepig.2010.04.012

A series of electrochromic materials were synthesized by incorporating the cathodic material viologen with anodic materials phenothiazine, indole, morpholine, pyrrole and carbazole, respectively. Their electrochemical and electrochromic properties were investigated by cyclic voltammetry and UV–Visible spectrophotometer. Electrochromic devices based on these compounds were fabricated with an active area of 2 cm × 4 cm which exhibited colorless-wine-blue multicolor electrochromism. Their color and bleach reversibility was excellent with high coloration efficiency after 100 cyclic voltammetry. The response times for the coloring and bleaching processes were less than 150 ms and 2 s respectively, and the dominant response speed significantly exceeded that of viologen alone. Their remarkable electrochromic behaviour and high stability render these electrochromic materials excellent candidates for applications in electrochromic devices.

Cysteine-Based Organocatalysts for the Highly Efficient Direct Stoichiometric anti- and syn-Aldol Reactions

Co-reporter:Shi Li, Chuanlong Wu, Xiangkai Fu, and Qiang Miao

Industrial & Engineering Chemistry Research 2011 Volume 50(Issue 24) pp:13711-13716

Publication Date(Web):October 29, 2011

DOI:10.1021/ie201482c

A series of cysteine-based organocatalysts have been designed and synthesized from a simple step. The anti-aldol and syn-aldol products could be obtained with up to 98:2 anti/syn and 99% ee; the stoichiometric ratio between aldehydes and ketones is 1. This catalyst could be easily recovered and efficiently used in large-scale reactions, which demonstrates its potential application in industry.

A Highly Efficient, Large-Scale, Asymmetric Direct Aldol Reaction Employing Simple Threonine Derivatives as Recoverable Organocatalysts in the Presence of Water

Co-reporter:Chuanlong Wu;Xiangkai Fu ;Shi Li

European Journal of Organic Chemistry 2011 Volume 2011( Issue 7) pp:1291-1299

Publication Date(Web):

DOI:10.1002/ejoc.201001396

Abstract

A one-step O-acylation of threonine resulted in a simple and readily available threonine-surfactant organocatalyst that could efficiently catalyze the direct asymmetric aldol reactions of cyclic and acyclic ketones with a series of aromatic aldehydes in the presence of water at room temperature with good yields (up to 99 %), diastereoselectivities (up to 99:1), and enantiomeric excesses (>99 %). The catalyst can beeasily recovered and reused with no decrease of enantioselectivity after six cycles. This novel catalyst can be efficiently used in large-scale reactions, with the enantioselectivity being maintained at the same level, which offers great possibilities for application in industry.

Synthesis of a new star-shaped 4,4′-bipyridine derivative and its multicolor solid electrochromic devices

Co-reporter:Gang Wang, Xiangkai Fu, Jing Huang, Chuanlong Wu, Liu Wu, Qiuliang Du

Organic Electronics 2011 Volume 12(Issue 7) pp:1216-1222

Publication Date(Web):July 2011

DOI:10.1016/j.orgel.2011.03.040

A new star-shaped 4,4′-bipyridine derivative (1,3,5-tri(1-methyl-4,4′-bipyridinium bromide)-2,4,6-trimethyl benzene) TBTB was synthesized and characterized. The electrochromic behavior, electrochromic mechanism and electro-optical properties of the new type of monosubstituted 4,4′-bipyridine derivative were investigated by cyclic voltammetry and UV–vis absorption spectra. Moreover, a serial of environmentally friendly solid electrochromic devices (ECD) based on TBTB were constructed successfully and their electrochromic performance were further studied. The ECD presented a stable as well as multicolor electrochromic change from blue to violet–blue and then to violet–red between 0 V and +3.0 V. They exhibited a fast switching time (∼0.3 s for coloring and ∼0.5 s for bleaching) between the violet–blue (+2.0 V) reduced state and the transparent light blue oxidized state (−2.0 V), with a contrast ranging from 25% to 40% at 530 nm and a coloration efficiency of 279 cm2 C−1.Graphical abstractThe ECD based on TBTB presented multicolor electrochromic change from blue to violet–blue and then to violet–red between 0 V and +3.0 V, corresponding to the four redox states, respectively.Highlights► A new star-shaped 4,4′-bipyridine derivative was synthesized and characterized. ► The solid ECD presented a stable as well as multicolor electrochromic change. ► The accepting-donating electron mechanism of the ECD was proposed and discussed. ► The ECD exhibited a fast switching time, with good contrast and coloration efficiency.

Synthesis, electrochemical and fluorescence properties of three new dithienylpyrroles bearing aromatic amine units

Co-reporter:Gang Wang, Xiangkai Fu, Jing Huang, Liu Wu, Jun Deng

Journal of Electroanalytical Chemistry 2011 Volume 661(Issue 2) pp:351-358

Publication Date(Web):15 October 2011

DOI:10.1016/j.jelechem.2011.08.016

Three new kinds of dithienylpyrroles derivatives bearing aromatic amine units were successfully synthesized by the Knorr–Paal condensation. The corresponding polymer films were also successfully prepared on ITO working electrode via electropolymerization in a low concentration containing 0.2 mM monomer in 0.01 M tetrabutylammonium perchlorate/dichloromethane solution. The electrochemical, surface morphology, thermal stability, spectroelectrochemistry properties and electrochromic behavior of the three polymer films were further investigated by cyclic voltammetry, scanning electron microscopy, thermogravimetric analysis, UV–vis absorption. The results demonstrated that the three electroactive polymer films possessed low optical band gap (Eg < 2.3 eV), smooth film surface, thermal stability (up to nearly 200 °C). All of the three polymer films presented a stable and well-defined reversible redox process as well as multicolor electrochromic change mainly from yellow green (in the reduced state) to grey green (in the neutral state) and then to blue (in the oxidized state).Highlights► Three new kinds of dithienylpyrroles derivatives were successfully synthesized. ► Their polymer films were successfully synthesized via electropolymerization. ► They possessed low optical band gap, smooth surface, thermal stability. ► They presented a good reversible redox process and multicolor electrochromic change.

Novel organic polymer–inorganic hybrid material zinc poly(styrene-phenylvinylphosphonate)-phosphate prepared with a simple method

Co-reporter:Jing Huang, Xiangkai Fu, Gang Wang, Qiang Miao

Journal of Solid State Chemistry 2011 Volume 184(Issue 9) pp:2605-2609

Publication Date(Web):September 2011

DOI:10.1016/j.jssc.2011.06.026

A novel type of organic polymer–inorganic hybrid material layered crystalline zinc poly(styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPP) was synthesized under mild conditions in the absence of any template. And the ZnPS-PVPP were characterized by FT-IR, diffusion reflection UV–vis, AAS, N2 volumetric adsorption, SEM, TEM and TG. Notably, this method was entirely different from the traditional means used for preparing other zinc phosphonate. Moreover, it could be deduced that ZnPS-PVPP possessed the potential applications for catalyst supports. In the initial catalytic tests, the catalysts immobilized onto ZnPS-PVPP showed comparable or higher activity and enantioselectivity with that of catalysts reported by our group in the asymmetric epoxidation of unfunctional olefins.Graphical AbstractZinc poly(styrene-phenylvinylphosphonate)-phosphate was a novel type of layered crystalline organic polymer–inorganic hybrid material prepared under mild conditions without addition of any template and could be used as heterogeneous catalyst supports.Highlights► New types of layered crystalline inorganic–organic polymer hybrid materials zinc poly(styrene-phenylvinylphosphonate–phosphate(ZnPS-PVPP)). ► ZnPS-PVPP prepared under mild condition without adding of any template. ► Immobilized chiral salen Mn (III) catalysts on ZnPS-PVPP supports show comparative activity and enantioselectivity with that of on ZSPP or ZPS-PVPA.

Olefin epoxidation catalyzed by Schiff base molybdenum (VI) complexes immobilized onto zirconium poly (styrene-phenylvinylphosphonate)-phosphate

Co-reporter:Zhongkai Hu, Xiangkai Fu, Yuedong Li

Inorganic Chemistry Communications 2011 Volume 14(Issue 3) pp:497-501

Publication Date(Web):March 2011

DOI:10.1016/j.inoche.2011.01.010

Schiff base molybdenum (VI) complexes were immobilized onto a novel polymer–inorganic hybrid support-zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA). The immobilized catalysts were well characterized by IR, BET, XPS, SEM and TEM. Compared with other heterogeneous catalysts known from the relative literatures, the as-prepared heterogeneous catalysts showed comparable or even higher conversion and chemical selectivity, which was mainly attributed to the special structure and composition of ZPS-PVPA. Moreover, the supported catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.Schiff base molybdenum (VI) complexes were immobilized onto a novel polymer–inorganic hybrid support-zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA). The immobilized catalysts were well characterized by IR, BET, XPS, SEM and TEM. Compared with other heterogeneous catalysts known from the relative literatures, the as-prepared heterogeneous catalysts showed comparable or even higher conversion and chemical selectivity, which was mainly attributed to the special structure and composition of ZPS-PVPA. Moreover, the supported catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.Research Highlights► Polystyrene–zirconium phosphate composite material (ZPS-PVPA) has special new characteristics, such as possessing caves, holes, micropores, channels and secondary channels with various sizes and shapes. ► Immobilized Schiff base molybdenum complexes show a promising application potential for epoxidation of unfunctionalized olefins. ► Our catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.

Highly efficient and excellent reusable catalysts of molybdenum(VI) complexes grafted on ZPS-PVPA for epoxidation of olefins with tert-BuOOH

Co-reporter:Zhongkai Hu;Xiangkai Fu;Yuedong Li;Xiaobo Tu

Applied Organometallic Chemistry 2011 Volume 25( Issue 2) pp:128-132

Publication Date(Web):

DOI:10.1002/aoc.1727

Abstract

Four new kinds of heterogeneous catalysts for olefins epoxidation were obtained by grafting diamines on organic polymer–inorganic hybrid material, zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA), and subsequently coordinating with Schiff base Mo(VI) complexes. The catalysts were characterized by IR, XPS, SEM and TEM. All catalysts were evaluated through the epoxidation of olefins using tert-BuOOH as oxidant. The heterogeneous catalysts possess the advantages of high conversion, selectivity and excellent reusability. The catalysts were easily separated from the reaction systems and could be reused 13 times without significant loss of catalytic activity. Copyright © 2010 John Wiley & Sons, Ltd.

A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate immobilized chiral salen Mn(III) catalyst large-scale asymmetric epoxidation of unfunctionalized olefins

Co-reporter:Xiaoyan Hu, Xiangkai Fu, Jiangwei Xu, Changwei Wang

Journal of Organometallic Chemistry 2011 696(15–16) pp: 2797-2804

Publication Date(Web):

DOI:10.1016/j.jorganchem.2011.04.027

New simple and recyclable O-acylation serine derivatives as highly enantioselective catalysts for the large-scale asymmetric direct aldol reactions in the presence of water

Co-reporter:Chuanlong Wu, Xiangkai Fu, Shi Li

Tetrahedron 2011 67(23) pp: 4283-4290

Publication Date(Web):

DOI:10.1016/j.tet.2011.03.083

Simple, inexpensive, and facile l-prolinamide used as a recyclable organocatalyst for highly efficient large-scale asymmetric direct aldol reactions

Co-reporter:Jiangwei Xu, Xiangkai Fu, Chuanlong Wu, Xiaoyan Hu

Tetrahedron: Asymmetry 2011 Volume 22(Issue 8) pp:840-850

Publication Date(Web):30 April 2011

DOI:10.1016/j.tetasy.2011.05.008

In order to discover a simple, inexpensive, and efficient route to obtain highly enantiomerically enriched anti-aldol products for applications in industry, a series of prolinamides 1–5 with different carbocyclic rings have been synthesized from achiral cycloalkylamine, and prolinamides 6–9 have been synthesized from aniline with different substituents. The organocatalysts obtained catalyzed the asymmetric aldol reaction and showed that no matter carbocyclic rings or aromatic rings were found to play a significant role in the formation of the aldol products. Moreover, the prolinamide 6 exhibited efficient catalytic activity in the asymmetric aldol reaction only with 5 mol % catalyst loading and 4 equiv of ketone, and afforded aldol products in high diastereoselectivity (up to anti/syn 99:1) and enantioselectivity (99%) and significantly enhanced the reaction yield (99%). These results were much better than l-proline-3-nitroanilide which had the strongest electron-withdrawing group on the aromatic ring. Furthermore, catalyst 6 can be easily recovered and reused, without a significant decrease of enantioselectivity after five cycles. This inexpensive, simple, and recyclable catalyst can be efficiently used in large-scale reactions with the enantioselectivities being maintained at the same level, which offers a great possibility for application in industry.(S)-N-Cyclopropyl-pyrrolidine-2-carboxamideC8H14N2O[α]D20=-66.2 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-Cyclopentyl-pyrrolidine-2-carboxamideC10H18N2O[α]D20=-53.9 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-Cyclohexyl-pyrrolidine-2-carboxamideC11H20N2O[α]D20=-60.5 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-Cycloheptyl-pyrrolidine-2-carboxamideC12H22N2O[α]D20=-45.6 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-cyclooctyl-pyrrolidine-2-carboxamideC13H24N2O[α]D20=-48.3 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-Phenyl-pyrrolidine-2-carboxamideC11H14N2O[α]D20=-44.2 (c 0.5, EtOH)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-(4-Methylphenyl) pyrrolidine-2-carboxamideC12H16N2O[α]D20=-58.9 (c 0.5, EtOH)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-(2,4-Dimethylphenyl) pyrrolidine-2-carboxamideC13H18N2O[α]D20=-62.8 (c 0.5, EtOH)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-(3-Nitrophenyl) pyrrolidine-2-carboxamideC11H13N3O3[α]D20=-41.1 (c 0.5, EtOH)Source of chirality: l-prolineAbsolute configuration: (2S)(S)-N-n-Hexyl-pyrrolidine-2-carboxamideC11H22N2O[α]D20=-48.6 (c 1, CHCl3)Source of chirality: l-prolineAbsolute configuration: (2S)

Simple and inexpensive threonine-based organocatalysts for the highly diastereo- and enantioselective direct large-scale syn-aldol and anti-Mannich reactions of α-hydroxyacetone

Co-reporter:Chuanlong Wu, Xiangkai Fu, Shi Li

Tetrahedron: Asymmetry 2011 Volume 22(Issue 10) pp:1063-1073

Publication Date(Web):31 May 2011

DOI:10.1016/j.tetasy.2011.06.022

Simple and inexpensive threonine-based organocatalysts that promote syn-aldol reactions and three-component asymmetric anti-Mannich reactions of α-hydroxyacetone achieving a respectable level of enantioselectivities are reported. The syn-aldol products could be obtained with up to a 99:1 syn/anti ratio and >99% ee while the anti-Mannich products could be obtained with up to a 96:4 anti/syn ratio and >99% ee. Catalyst 1c can be used efficiently on a large-scale with the enantioselectivities of the syn-aldol and anti-Mannich reactions being maintained at the same level, which offers a great possibility for application in industry.(2S,3R)-O-(n-Butyryl)-l-threonineC8H15NO4[α]D20=+16.1 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Hexanoyl)-l-threonineC10H19NO4[α]D20=+15.0 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Octanoyl)-l-threonineC12H23NO4[α]D20=+13.2 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Decanoyl)-l-threonineC14H27NO4[α]D20=+13.0 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n- Dodecanoyl)-l-threonineC16H31NO4[α]D20=+11.6 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(Benzoyloxy)-l-threonineC11H13NO4[α]D20=-12.8 (c 1.02, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(Cyclohexylcarbonyl)-l-threonineC11H19NO4[α]D20=+15.7 (c 1.1, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(1-Adamantylcarbonyl)-l-threonineC15H23NO4[α]D20=+5.4 (c 1.2, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)

Simple and Facile l-Prolinamides Derived from Achiral Cycloalkylamines as Organocatalysts for the Highly Efficient Large-Scale Asymmetric Direct Aldol Reactions

Co-reporter:Jiang-Wei Xu;Xiao-Yan Hu;Chuan-Long Wu

Catalysis Letters 2011 Volume 141( Issue 8) pp:1156-1163

Publication Date(Web):2011 August

DOI:10.1007/s10562-011-0585-3

A series of N-cycloalkylprolinamides have been designed and synthesized from achiral cycloalkylamines in a facile manner. They promoted high stereoselectivity in the cross-aldol reaction. N-cyclopropylprolinamide performed best with a smallest carbocyclic ring, and the anti-aldol products could be obtained with up to 99:1 anti/syn and 99% ee. Carbocyclic ring was found to play a significant role in the formation of the aldol products. This simple catalyst can be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offers great possibility for applications in industry.All of the catalysts 1a–e synthesized from achiral cycloalkylamines in a facile manner and their catalytic properties were studied in depth for the first time. All of the catalysts 1a–e exhibited great catalytic activity in the asymmetric aldol reaction in m-xylene using acetic acid as cocatalyst at −20 °C with only 5 mol% catalyst loading in 4 equivalents ketone, and the anti-aldol products could be obtained with up to 99:1 anti/syn and 99% ee. Compared with proline and prolinamide 1f, it is easily found that the carbocyclic ring of N-cycloalkyl-l-prolinamide could be anticipated in some way to enhance the enantioselectivity in m-xylene at low temperature. The results observed for 1a surpass those reported so far for simple prolinamide derivatives and are comparable to those for organocatalysts of much more structural complexity. Catalyst 1a can be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offers great possibility for applications in industry.

Synthesis of a Novel Zirconium Oligostyrenylphosphonate-Phosphate and its Application in Asymmetric Epoxidation

Co-reporter:Yunfei Luo;Xiangkai Fu;Xiaochuan Zou

Journal of Inorganic and Organometallic Polymers and Materials 2011 Volume 21( Issue 2) pp:276-282

Publication Date(Web):2011 June

DOI:10.1007/s10904-010-9447-5

The layered crystalline zirconium oligostyrenylphosphonate-phosphate (LCZSPP) was synthesized in the presence of HF for the first time, and this compound was well characterized by FT-IR, TG, SEM, TEM, XPS and XRD. The LCZSPP possessed high thermal stability by TG. SEM and TEM demonstrated that this compound is a typically layered crystalline compound with basically regular shape. XRD data also showed that the interlayer spacing (10.65 Å) of the sample was 3.01 Å more than the α-ZrP (7.64 Å). Moreover, chiral Jacobsen’s catalyst was axially immobilized onto LCZSPP by a diamine linker group. All the synthesized heterogeneous catalysts exhibited excellent reactivity and enantioselectivity in the asymmetric epoxidation of simple olefins.

Highly Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Chiral Jacobsens Catalyst Immobilized on Phenoxy-Modified Zirconium Poly(syrene-phenylvinylphos- phonate)phosphate

Co-reporter:Xiaochuan Zou;Xiangkai Fu;Yuedong Li;Xiaobo Tu;Shaodong Fu;Yunfei Luo ;Xiaoju Wu

Advanced Synthesis & Catalysis 2010 Volume 352( Issue 1) pp:163-170

Publication Date(Web):

DOI:10.1002/adsc.200900424

Abstract

Chiral Jacobsen’s catalyst was axially immobilized onto phenoxy-modified zirconium poly(styrene-phenylvinylphosphonate)phosphate (ZPS-PVPA). The immobilized catalysts show comparable ee values for asymmetric epoxidation of styrene and much higher ee values for α-methylstyrene (73.7% vs. 54.0%) and indene (99.9% vs. 65.0%) than the homogeneous Jacobsen’s catalyst. Moreover, the as-synthesized catalysts are relatively stable and can be recycled at least five times without significant loss of activity and enantioselectivity. A point worth emphasizing is that the heterogeneous catalysts afforded remarkable increases of conversion and ee values in the absence of expensive O-coordinating axial bases for the asymmetric epoxidation of olefins, especially for the epoxidation of α-methylstyrene (conversion: from 24.3% to 99.9%; ee: from 29.4% to 73.7%), which may overcome the last obstacle for the potential industry application of chiral Jacobsen’s catalyst.

Synthesis and spectroelectrochemical properties of two new dithienylpyrroles bearing anthraquinone units and their polymer films

Co-reporter:Gang Wang, Xiangkai Fu, Jing Huang, Liu Wu, Qiuliang Du

Electrochimica Acta 2010 Volume 55(Issue 23) pp:6933-6940

Publication Date(Web):30 September 2010

DOI:10.1016/j.electacta.2010.07.012

Two new kinds of dithienylpyrroles bearing anthraquinone units have been prepared by the Knorr–Paal condensation between 1,4-di(thiophen-2-yl)butane-1,4-dione and 1-/2-amino-anthraquinone. The corresponding polymer films were successfully synthesized via electropolymerization. The electrochemical, electro-optical properties and electrochromic behavior of the two polymer films were further investigated by thermogravimetric analysis, cyclic voltammetry and UV–vis absorption spectra. The results demonstrated that the two polymer films were thermally stable up to nearly 300 °C. Both the two electroactive polymer films presented a stable and well-defined reversible redox process as well as multicolor electrochromic change from yellow (in the reduced state) to grey (in the neutral state) and then to blue (in the oxidized state).

Threonine-surfactant organocatalysts for the highly diastereo- and enantioselective direct anti-Mannich reactions of hydroxyacetone

Co-reporter:Chuanlong Wu, Xiangkai Fu, Xuebing Ma, Shi Li, Chao Li

Tetrahedron Letters 2010 Volume 51(Issue 44) pp:5775-5777

Publication Date(Web):3 November 2010

DOI:10.1016/j.tetlet.2010.08.085

In this work, several new l-threonine derivatives as organocatalysts were synthesized in one step for the first time by the reaction of threonine with acyl chlorides at room temperature in trifluoroacetic acid on a large-scale without protecting groups involved or chromatographic techniques, and those threonine-surfactant organocatalysts mediated the direct asymmetric anti-Mannich reactions of hydroxyacetone and anilines with aldehydes to synthesize anti-1,2-amino alcohols in good yields (75–93%) and highly enantioselectivities (up to 99% ee).

Chiral salen Mn(III) immobilized on sulfoalkyl modified ZSP-IPPA as an effective catalyst for asymmetric epoxidation of unfunctionalized olefins

Co-reporter:Xiaobo Tu, Xiangkai Fu, Xiaoyan Hu, Yuedong Li

Inorganic Chemistry Communications 2010 Volume 13(Issue 3) pp:404-407

Publication Date(Web):March 2010

DOI:10.1016/j.inoche.2009.12.034

Sulfoalkyl modified zirconium poly (styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA), with special structures of new type of organic–inorganic hybrid material were designed and synthesized for immobilization of the chiral salen Mn(III) Jacobsen’s homogenous catalyst by axial coordination. All the heterogeneous chiral salen Mn(III) catalysts with different linkage lengths obtained exhibited great catalytic activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. The influence of the linkage lengths on the catalytic performance was investigated. What’s more, the catalysts were easily separated from the reaction systems and could be reused for several times without significant loss of catalytic activity.Sulfoalkyl modified zirconium poly (styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA) were designed and synthesized for immobilization of the chiral homogenous salen Mn(III) catalyst by axial coordination. The linkage lengths of the sulfoalkyl modified ZPS-IPPA play an important role in ee values and yields of epoxidations. The heterogeneous catalysts are relatively stable and can be recycled nine times.

One-step, efficient synthesis of combined threonine–surfactant organocatalysts for the highly enantioselective direct aldol reactions of cyclic ketones with aromatic aldehydes in the presence of water

Co-reporter:Chuanlong Wu, Xiangkai Fu, Xuebing Ma, Shi Li

Tetrahedron: Asymmetry 2010 Volume 21(Issue 20) pp:2465-2470

Publication Date(Web):28 October 2010

DOI:10.1016/j.tetasy.2010.09.006

In this work, a new class of organocatalysts have been designed and synthesized in one step by a rational combination of threonine with acyl chlorides at room temperature in trifluoroacetic acid to make a series of novel combined threonine-surfactant organocatalysts readily available on a large-scale. No protecting groups or chromatographic techniques are involved in the procedures, while certain combined threonine-surfactant organocatalysts mediate the direct aldol reactions of cyclic ketones with aromatic aldehydes to provide the aldol products in good yields with enantioselectivities of up to 99%.(2S,3R)-O-(n-Butyl)-l-threonine hydrochlorideC8H16ClNO4[α]D20=+16.1 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Hexanoyl)-l-threonine hydrochlorideC10H20ClNO4[α]D20=+15.0 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Octanoyl)-l-threonine hydrochlorideC12H24ClNO4[α]D20=+13.2 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Decanoyl)-l-threonine hydrochlorideC14H28ClNO4[α]D20=+13.0 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Dodecanoyl)-l-threonine hydrochlorideC16H32ClNO4[α]D20=+11.6 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Palmitoyl)-l-threonine hydrochlorideC20H40ClNO4[α]D20=+7.8 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)(2S,3R)-O-(n-Stearoyl)-l-threonine hydrochlorideC22H44ClNO4[α]D20=+8.0 (c 1.0, MeOH)Source of chirality: (2S,3R)-threonineAbsolute configuration: (2S,3R)

Synthesis of novel immobilized tridentate Schiff base dioxomolybdenum(VI) complexes as efficient and reusable catalysts for epoxidation of unfunctionalized olefins

Co-reporter:Yuedong Li, Xiangkai Fu, Biwei Gong, Xiaochuan Zou, Xiaobo Tu, Junxian Chen

Journal of Molecular Catalysis A: Chemical 2010 322(1–2) pp: 55-62

Publication Date(Web):

DOI:10.1016/j.molcata.2010.02.015

The synthesis and electrochemical properties of anodic electrochromic materials phenothiazine derivatives and their electrochromic devices

Co-reporter:Xi Tu, Xiangkai Fu, Qinglong Jiang

Displays 2010 Volume 31(Issue 3) pp:150-154

Publication Date(Web):July 2010

DOI:10.1016/j.displa.2010.05.001

In order to develop novel electrochromic materials, a series of N-substituted phenothiazine derivatives (PDs) were synthesized via SN2 reaction and characterized by NMR, IR spectroscopy. Their electrochemical properties were investigated using cyclic voltammetry and their spectrochemical properties were examined by UV–vis spectroscopy. It was found that phenothiazine derivatives in electrochromic devices (ECDs) showed reversible, clear color changes on electrochemical process. An electrochromic effect was observed with a color change from colorless to red or green for the phenothiazine derivatives synthesized. The phenothiazine derivatives synthesized are promising candidate for visible electrochromic devices, for their outstanding electrochromic behaviors plus the inexpensive starting materials and short synthetic routes.

The copper(I) iodide accelerated synthesis of mono- and bisbenzyl substituted 1- and 2-aminoanthraquinones

Co-reporter:Binglin Sui, Xiangkai Fu

Dyes and Pigments 2009 Volume 83(Issue 1) pp:1-6

Publication Date(Web):October 2009

DOI:10.1016/j.dyepig.2009.01.004

A series of novel, monobenzyl substituted, 1-aminoanthraquinones, monobenzyl substituted 2-aminoanthraquinones and bisbenzyl substituted 2-aminoanthraquinones were synthesized via the benzylation of 1-/2-aminoanthraquinone, respectively. The benzyl substituted aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry; their electrochemical properties were investigated using cyclic voltammogram and their spectrochemical properties were determined using UV–vis spectroscopy in dichloromethane. Copper(I) iodide, in conjunction with 1,10-phenanthroline as ligand, accelerates the reaction rate and enhances reaction yields by ∼30%. The benzyl substituted aminoanthraquinone derivatives are redox active and potentially useful as electrochromic materials as well as for biological and pharmaceutical studies.

Highly diastereo- and enantioselective direct aldol reactions by 4-tert-butyldimethylsiloxy-substituted organocatalysts derived from N-prolylsulfonamides in water

Co-reporter:Shao-dong Fu, Xiang-kai Fu, Shu-peng Zhang, Xiao-chuan Zou, Xiao-ju Wu

Tetrahedron: Asymmetry 2009 Volume 20(Issue 20) pp:2390-2396

Publication Date(Web):20 October 2009

DOI:10.1016/j.tetasy.2009.09.019

Novel application of 1-/2-phenyl substituted 9,10-anthraquinones in solid electrochromic devices

Co-reporter:Binglin Sui;Xiangkai Fu

Journal of Solid State Electrochemistry 2009 Volume 13( Issue 12) pp:

Publication Date(Web):2009 December

DOI:10.1007/s10008-008-0767-0

1-/2-phenyl substituted 9,10-anthraquinones were synthesized via Suzuki coupling reactions of 1-/2-iodo-9,10-anthraquinones with benzeneboronic acid. They are efficient and reversible electrochromic materials and their solid electrochromic devices were prepared. When reduced, the device color of 1-phenyl-9,10-anthraquinone shifts from yellow to claret while that of 2-phenyl-9,10-anthraquinone switches from yellow-green to a dark blue-purple. Their different characteristics and behaviors in electrochromic devices are only determined by the different substituted positions of the phenyl group. They are potentially to be widely applied in commercial application for the excellent behaviors plus the inexpensive starting materials and short synthetic routes.

Chiral Mn (III) salen complexes covalently bonded on zirconium oligostyrenylphosphonate-phosphates as catalysts for enantioselective epoxidation of nonfunctionalized alkenes

Co-reporter:Wenshan Ren, Xiangkai Fu

Journal of Molecular Catalysis A: Chemical 2009 312(1–2) pp: 40-47

Publication Date(Web):

DOI:10.1016/j.molcata.2009.07.002

Rationally designed 4-phenoxy substituted prolinamide phenols organocatalyst for the direct aldol reaction in water

Co-reporter:Shu-peng Zhang, Xiang-kai Fu, Shao-dong Fu

Tetrahedron Letters 2009 50(11) pp: 1173-1176

Publication Date(Web):

DOI:10.1016/j.tetlet.2008.10.120

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

Co-reporter:Xiang-Kai FU;Yong-Feng GONG;Shu-Peng ZHANG;Qing-Long JIANG

Chinese Journal of Chemistry 2007 Volume 25(Issue 11) pp:1743-1747

Publication Date(Web):13 NOV 2007

DOI:10.1002/cjoc.200790322

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ¹H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83×10⁻⁴S·cm⁻¹ at room temperature. Thermogravimetry (TG) of the polymer electrolyte showed that the thermal stability was up to at least 150 °C. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochromic devices.

Spectroscopic and electrochemical studies on block-polymer/PMMA blend based composite polymer electrolytes

Co-reporter:Yongfeng Gong;Shupeng Zhang;Xiangkai Fu

Journal of Applied Polymer Science 2007 Volume 106(Issue 6) pp:4091-4097

Publication Date(Web):5 SEP 2007

DOI:10.1002/app.26903

Poly(methylmethacrylate)(PMMA)/oxymethylene-linked polyoxyethylene multi-block polymer(Om-POE_n, where n represents number of unit CH₂CH₂O) blend based composite electrolyte films containing different lithium salt concentration and nanofillers' content are prepared using solvent evaporation technique. The interaction of polymer–salt complex has been confirmed using FTIR spectral studies. The figuration of CPE was studied by XRD. Ionic conductivity and thermal behavior of the CPEs were studied with various salt concentrations, temperature, and nanofillers' content. The surface structure of the CPE is also investigated using scanning electron microscopy. The high room temperature ionic conductivity, transmittivity in the visible region, and thermal stability make these CPEs potential candidates as solid-like electrolytes for electrochemical devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Synthesis of a new type of immobilized chiral salen Mn(III) complex as effective catalysts for asymmetric epoxidation of unfunctionalized olefins

Co-reporter:Biwei Gong, Xiangkai Fu, Junxian Chen, Yuedong Li, Xiaochuan Zou, Xiaobo Tu, Pingping Ding, Liping Ma

Journal of Catalysis (15 February 2009) Volume 262(Issue 1) pp:9-17

Publication Date(Web):15 February 2009

DOI:10.1016/j.jcat.2008.11.027

A new type of inorganic–organic hybrid materials—zirconium poly(styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) was designed and synthesized. A series of new heterogeneous catalysts was obtained by grafting diamine or polyamine on ZPS-PVPA and subsequently axial coordination with chiral salen Mn(III) complexes. All the synthesized heterogeneous catalysts exhibited great activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Especially, in the epoxidation of α-methylstyrene, both the conversion and enantiometric excess (ee) could exceed 99%. Furthermore, the catalysts were conveniently separated from the reaction system by simple precipitation in hexane and could be reused at least ten times without significant loss of activity and enantioselectivity.New types of ZAMPS-PVPA-immobilized chiral salen Mn(III) complexes were synthesized and used as catalysts in the asymmetric epoxidation of unfunctionalized olefins.Download high-res image (44KB)Download full-size image

Chiral salen Mn(III) complexes immobilized onto crystalline aluminium oligo-styrenyl phosphonate-hydrogen phosphate (AlSPP) for heterogeneous asymmetric epoxidation

Co-reporter:Xuemei Huang, Xiangkai Fu, Ziyong Jia, Qiang Miao and Guoming Wang

Catalysis Science & Technology (2011-Present) 2013 - vol. 3(Issue 2) pp:NaN424-424

Publication Date(Web):2012/09/14

DOI:10.1039/C2CY20394D

Highly efficient direct large-scale stoichiometric aldol reactions catalyzed by a new diamine salt in the presence of water

Co-reporter:Jing Huang, Guodong Chen, Xiangkai Fu, Chao Li, Chuanlong Wu and Qiang Miao

Catalysis Science & Technology (2011-Present) 2012 - vol. 2(Issue 3) pp:NaN553-553

Publication Date(Web):2011/12/05

DOI:10.1039/C1CY00318F

Co-reporter:Jing Huang, Xiangkai Fu, Gang Wang, Yaqin Ge and Qiang Miao

Catalysis Science & Technology (2011-Present) 2012 - vol. 2(Issue 5) pp:NaN1050-1050