Ji-Chang Xiao

The sulfinatodehalogenation reaction represents one of the most important methodologies to incorporate fluorine into organic molecules. Using inexpensive sulfur-containing reactants such as Na2S2O4 under mild conditions, per- and polyfluoroalkyl halides (RFX, X = Br, I, CCl3) can be transformed smoothly into the corresponding sulfinate salts. This method is also used for the perfluoroalkylation of alkenes, dienes, alkynes and aromatics. Notably, after 1998, the sulfinatodehalogenation of perfluoroalkyl chlorides (RFCl) has been realized by using dimethylsulfoxide (DMSO) as a solvent instead of CH3CN/H2O in the Na2S2O4/NaHCO3 initiation system. Perfluoroalkyl chlorides, ethyl chlorofluoroacetates and chlorodifluoroacetates, and even nonfluorinated compounds, such as ethyl chloro- or dichloroacetates and chloroform, were either converted into the corresponding sulfinate salts or alkylated alkenes, alkynes and aromatics (including porphyrins). The sulfinatodehalogenation reaction has remarkable advantages. With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, we believe that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.

Efficient synthesis of 1-alkyl-3-methylimidazolium fluorides and possibility of the existence of hydrogen bonding between fluoride anion and C(sp3)–H

Co-reporter:Zhi-Qiang Zhu, Ming-Yue Jiang, Chang-Ge Zheng, Ji-Chang Xiao

Journal of Fluorine Chemistry 2012 Volume 133() pp:160-162

Publication Date(Web):January 2012

DOI:10.1016/j.jfluchem.2011.08.003

1-Alkyl-3-methylimidazolium fluorides were successfully synthesized by the reaction of silver fluoride with the corresponding imidazolium iodides.Graphical abstract1-Alkyl-3-methylimidazolium fluorides were successfully synthesized by the reaction of silver fluoride with the corresponding imidazolium iodides. Weak interaction between fluoride anion and C(sp3)–H was observed as determined by single crystal X-ray diffraction analysis.Highlights► 1-Alkyl-3-methylimidazolium fluorides was first synthesized from the reaction of silver fluoride with imidazolium iodides. ► We conducted the NMR and the single crystal X-ray analysis. ► Weak interaction was observed between fluoride anion and C(sp3)–H.

Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts

Co-reporter:Cheng-Pan Zhang, Ji Cai, Chang-Bing Zhou, Xiao-Ping Wang, Xing Zheng, Yu-Cheng Gu and Ji-Chang Xiao

Chemical Communications 2011 vol. 47(Issue 33) pp:9516-9518

Publication Date(Web):19 Jul 2011

DOI:10.1039/C1CC13460D

The ligand-free trifluoromethylation of arylboronic acids with a [Ph2SCF3]+[OTf]−/Cu(0) system has been carefully investigated. Aryl-, alkenyl- and heteroarylboronic acids with a variety of functional groups were suitable substrates for this reaction. It is suggested that a CuCF3 species is formed under the reaction conditions.

Chiral N-heterocyclic carbene catalyzed annulation of α,β-unsaturated aldehydes with 1,3-dicarbonyls

Co-reporter:Zhi-Qiang Zhu, Xing-Liang Zheng, Ning-Fei Jiang, Xiaolong Wan and Ji-Chang Xiao

Chemical Communications 2011 vol. 47(Issue 30) pp:8670-8672

Publication Date(Web):27 Jun 2011

DOI:10.1039/C1CC12778K

Chiral N-heterocyclic carbene catalyzed annulations of ynals and enals with 1,3-dicarbonyls have been described. The two reactions provided direct and efficient methods for enantioselective synthesis of functionalized dihydropyranones. Comparatively, the reactions starting from ynals were atom-economical; furthermore the reactions of enals demonstrated broader substrate compatibility.

Generation of the CF3 radical from trifluoromethylsulfonium triflate and its trifluoromethylation of styrenes

Co-reporter:Cheng-Pan Zhang, Zong-Ling Wang, Qing-Yun Chen, Chun-Tao Zhang, Yu-Cheng Gu and Ji-Chang Xiao

Chemical Communications 2011 vol. 47(Issue 23) pp:6632-6634

Publication Date(Web):11 May 2011

DOI:10.1039/C1CC11765C

The CF3 radical was generated from the reaction of S-(trifluoromethyl)diphenylsulfonium triflate with Na2S2O4 or HOCH2SO2Na under suitable conditions without further reduction. Based on this, a method for the synthesis of α-trifluoromethylated ketones has been successfully developed.

The Asymmetric FriedelCrafts Reaction of Indoles with Fluoroalkylated Nitroalkenes Catalyzed by Chiral Phosphoric Acid

Co-reporter:Jin-Hong Lin

European Journal of Organic Chemistry 2011 Volume 2011( Issue 24) pp:4536-4539

Publication Date(Web):

DOI:10.1002/ejoc.201100683

Abstract

The enantioselective Friedel–Crafts fluoroalkylation of indoles with fluoroalkylated nitroalkenes, catalyzed by chiral phosphoric acid is described. The regioselectivity of fluoroalkylated nitroalkenes is a problem worth discussing, and it was found that the carbon atom adjacent to the fluoroalkyl group is more reactive than that adjacent to NO₂ group.

Corrigendum to “Thermal rearrangement of substituted difluoro(methylene)cyclopropane” [J. Fluorine Chem. 132 (2011) 63–67]

Co-reporter:Xiao-Chun Hang, Wei-Peng Gu, Qing-Yun Chen, Ji-Chang Xiao, Wei-Guo Xu, Shubin Liu

Journal of Fluorine Chemistry 2011 Volume 132(Issue 4) pp:302

Publication Date(Web):April 2011

DOI:10.1016/j.jfluchem.2011.02.011

Thermal rearrangement of substituted difluoro(methylene)cyclopropane

Co-reporter:Xiao-Chun Hang, Wei-Peng Gu, Qing-Yun Chen, Ji-Chang Xiao, Wei-Guo Xu, Shubin Liu

Journal of Fluorine Chemistry 2011 Volume 132(Issue 1) pp:63-67

Publication Date(Web):January 2011

DOI:10.1016/j.jfluchem.2010.11.007

Both experimental and computational approaches have been employed in the present work to investigate the thermal conversion of substituted difluoro(methylene)cyclopropanes (F2MCP) E-1,1-difluoro-2,2-dimethyl-3-tosylmethylene cyclopropane 1, to the thermodynamically more stable F2MCP products, 1,1-difluoro-2-tosyl-3-(propan-2-ylidene)cyclopropane 2, and 1-(3-(difluoromethylene)-2,2-dimethylcyclopropylsulfonyl)-4-methylbenzene 3. The X-ray crystal structure has been obtained for both 1 and 2, respectively, based on which theoretical analyses on their structure and stability have been carried out. Possible reaction mechanisms are proposed.Graphical abstractResearch highlights▶ Thermal rearrangement of difluoro(methylene)cyclopropane was found. ▶ Theoretical calculations revealed that the rearrangement favors a polar pathway. ▶ Difluorocarbene addition to double bond is a kinetically controlled process.

Copper-Mediated Trifluoromethylation of Heteroaromatic Compounds by Trifluoromethyl Sulfonium Salts

Co-reporter:Cheng-Pan Zhang;Zong-Ling Wang;Dr. Qing-Yun Chen;Chun-Tao Zhang;Dr. Yu-Cheng Gu;Dr. Ji-Chang Xiao

Angewandte Chemie International Edition 2011 Volume 50( Issue 8) pp:1896-1900

Publication Date(Web):

DOI:10.1002/anie.201006823

Copper-Mediated Trifluoromethylation of Heteroaromatic Compounds by Trifluoromethyl Sulfonium Salts

Co-reporter:Cheng-Pan Zhang;Zong-Ling Wang;Dr. Qing-Yun Chen;Chun-Tao Zhang;Dr. Yu-Cheng Gu;Dr. Ji-Chang Xiao

Angewandte Chemie 2011 Volume 123( Issue 8) pp:1936-1940

Publication Date(Web):

DOI:10.1002/ange.201006823

N-Heterocyclic Carbene-Catalyzed Reaction of Alkynyl Aldehydes with 1,3-Keto Esters or 1,3-Diketones

Co-reporter:Zhi-Qiang Zhu

Advanced Synthesis & Catalysis 2010 Volume 352( Issue 14-15) pp:2455-2458

Publication Date(Web):

DOI:10.1002/adsc.201000240

Abstract

The N-heterocyclic carbene-catalyzed reaction of alkynyl aldehydes with 1,3-keto esters or 1,3-diketones has been studied. This protocol offers an entirely new, mild and atom-economical access to highly functionalized 3,4-dihydropyranones.

Synthesis and Physicochemical Properties of Bis(fluoroalkanesulfon)amide-Based Ionic Liquids

Co-reporter:Cheng-Pan Zhang;Zong-Ling Wang;Qing-Yun Chen;Chun-Tao Zhang;Yu-Cheng Gu

European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 22) pp:3419-3422

Publication Date(Web):

DOI:10.1002/ejic.201000171

Abstract

A series of bis(fluoroalkanesulfon)amides were synthesized in good yield from the reaction of fluoroalkanesulfonamides and fluoroalkylsulfonyl fluorides. Ionic liquids based on these amide anions and an imidazolium cation demonstrated high densities and a wide temperature range for the liquid state.

One-pot synthesis of arylfluoroalkylsulfoxides and study of their anomalous 19F NMR behavior

Co-reporter:Cheng-Pan Zhang, Zong-Ling Wang, Qing-Yun Chen, Chun-Tao Zhang, Ji-Chang Xiao

Journal of Fluorine Chemistry 2010 Volume 131(Issue 3) pp:433-438

Publication Date(Web):March 2010

DOI:10.1016/j.jfluchem.2009.12.019

Arylfluoroalkylsulfoxides were successfully synthesized in one-pot when fluoroalkylsulfinate reacted with benzene and triflic anhydride in triflic acid and dichloromethane as the medium. The characteristics of their 19F NMR spectra were examined and analyzed for these structures. Electronic and steric effects of substituents at α- or β-position were revealed to be the main cause of the anomalous behavior of their chemical shifts and coupling constants. Interactions between arylfluoroalkylsulfoxides and solvents were also investigated and discussed.Arylfluoroalkylsulfoxides were successfully synthesized in one-pot when fluoroalkylsulfinate reacted with benzene and triflic anhydride in triflic acid and dichloromethane as the medium. The characteristics of their 19F NMR spectra were examined and analyzed for these structures. Electronic and steric effects of substituents at α- or β-position were revealed to be the main cause of the anomalous behavior of their chemical shifts and coupling constants. Interactions between arylfluoroalkylsulfoxides and solvents were also investigated and discussed.

Determination of pKa values of fluoroalkanesulfonamides and investigation of their nucleophilicity

Co-reporter:Cheng-Pan Zhang, Zong-Ling Wang, Qing-Yun Chen, Chun-Tao Zhang, Yu-Cheng Gu, Ji-Chang Xiao

Journal of Fluorine Chemistry 2010 Volume 131(Issue 7) pp:761-766

Publication Date(Web):July 2010

DOI:10.1016/j.jfluchem.2010.03.013

The pKa values of a series of fluoroalkanesulfonylamides were measured by potentiometric titration. Different kinds of alkyl halides and tosylates were employed to investigate the nucleophilicity of fluoroalkanesulfonylamides. Fluoroalkanesulfonylamides with longer fluoroalkyl chain have weaker nucleophilicity.The pKa values of a series of fluoroalkanesulfonylamides were measured by potentiometric titration. Different kinds of alkyl halides and tosylates were employed to investigate the nucleophilicity of fluoroalkanesulfonylamides. Fluoroalkanesulfonylamides with longer fluoroalkyl chain have weaker nucleophilicity.

Enantioselective aldol reaction of cyclic ketones with aryl aldehydes catalyzed by a cyclohexanediamine derived salt in the presence of water

Co-reporter:Jin-Hong Lin, Cheng-Pan Zhang and Ji-Chang Xiao

Green Chemistry 2009 vol. 11(Issue 11) pp:1750-1753

Publication Date(Web):11 Sep 2009

DOI:10.1039/B916583E

Water was found to be a suitable reaction medium for the direct asymmetric aldol reaction of various cyclic ketones with aryl aldehydes catalyzed by a primary-tertiary diamine-Brønsted acid.

The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators and an unexpected intramolecular nucleophilic substitution reactionvia a proposed Ni(III) NCP intermediate

Co-reporter:Hua-Wei Jiang, Qing-Yun Chen, Ji-Chang Xiao and Yu-Cheng Gu

Chemical Communications 2009 (Issue 25) pp:3732-3734

Publication Date(Web):15 May 2009

DOI:10.1039/B904615A

The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators resulted in an unexpected intramolecular nucleophilic substitution reactionvia a proposed Ni(III) NCP intermediate, which could be detected by HRMS.

Corrigendum to “A novel pyrrolidinium ionic liquid with 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel–Crafts alkylations of indoles with nitroalkenes” [J. Fluorine Chem. 130 (2009) 394–398]

Co-reporter:Jin-Hong Lin, Cheng-Pan Zhang, Zhi-Qiang Zhu, Qing-Yun Chen, Ji-Chang Xiao

Journal of Fluorine Chemistry 2009 Volume 130(Issue 6) pp:604

Publication Date(Web):June 2009

DOI:10.1016/j.jfluchem.2009.04.005

An Efficient Method for the Preparation of Pentafluoroiodoethane from Chloropentafluoroethane

Co-reporter:Chengpan ZHANG;Jinhong LIN;Zhenwei QIANG ;Jichang XIAO

Chinese Journal of Chemistry 2009 Volume 27( Issue 1) pp:202-204

Publication Date(Web):

DOI:10.1002/cjoc.200990019

Abstract

An efficient method was developed for the synthesis of pentafluoroiodoethane from chloropentafluoroethane. Sulfinatodechlorination of CF₃CF₂Cl was carefully investigated. Subsequent iodination can be conducted in one pot without further purification, giving the corresponding CF₃CF₂I in practically acceptable yield.

A mild hydrodehalogenation of fluoroalkyl halides

Co-reporter:Cheng-Pan Zhang, Qing-Yun Chen, Ji-Chang Xiao, Yu-Cheng Gu

Journal of Fluorine Chemistry 2009 Volume 130(Issue 7) pp:671-673

Publication Date(Web):July 2009

DOI:10.1016/j.jfluchem.2009.05.005

A mild hydrodehalogenation reaction of fluoroalkyl halides (RfCF2X, X = Br, I) has been developed under weakly basic conditions, giving the corresponding hydrogenolysis products with moderate to high yields.A mild hydrodehalogenation reaction of fluoroalkyl halides has been developed under weakly basic conditions, giving the corresponding hydrogenolysis products with moderate to high yields.

A novel pyrrolidinium ionic liquid with 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel–Crafts alkylations of indoles with nitroalkenes

Co-reporter:Jin-Hong Lin, Cheng-Pan Zhang, Zhi-Qiang Zhu, Qing-Yun Chen, Ji-Chang Xiao

Journal of Fluorine Chemistry 2009 Volume 130(Issue 4) pp:394-398

Publication Date(Web):April 2009

DOI:10.1016/j.jfluchem.2009.01.004

A series of pyrrolidinium-based salts with new fluorine-containing anions were synthesized. Different melting points could be obtained by changing the length of the fluoroalkyl chain of the anions. The pyrrolidinium 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate ([C4H8NH2][H(CF2)4O(CF2)2SO3]) is highly fluid even below room temperature. It can be used both as a recyclable solvent and as an efficient catalyst for Friedel–Crafts alkylations of indoles with nitroalkenes.A novel pyrrolidinium ionic liquid was used as both the recyclable solvent and catalyst for Friedel–Crafts alkylations of indoles with nitroalkenes.

Reaction of difluorocarbene with propargyl esters and efficient synthesis of difluorocyclopropyl ketones

Co-reporter:Xiao-Chun Hang, Wei-Peng Gu, Qing-Yun Chen, Ji-Chang Xiao

Tetrahedron 2009 65(32) pp: 6320-6324

Publication Date(Web):

DOI:10.1016/j.tet.2009.06.019

Synthesis and reactions of the first fluoroalkylated Ni(II) N-confused porphyrins

Co-reporter:Hua-Wei Jiang, Qing-Yun Chen, Ji-Chang Xiao and Yu-Cheng Gu

Chemical Communications 2008 (Issue 42) pp:5435-5437

Publication Date(Web):22 Sep 2008

DOI:10.1039/B811831K

The first fluoroalkylated Ni(II) N-confused porphyrins were synthesized with high regioselectivity and its further alkylation was studied.

Novel low-melting salts with donor–acceptor substituents as targets for second-order nonlinear optical applications

Co-reporter:Zhi-Qiang Zhu, Shaoji Xiang, Qing-Yun Chen, Chaosen Chen, Zhuo Zeng, Yi-Ping Cui and Ji-Chang Xiao

Chemical Communications 2008 (Issue 40) pp:5016-5018

Publication Date(Web):01 Sep 2008

DOI:10.1039/B810671A

We synthesized several novel low-melting ionic salts with donor–acceptor substituents and investigated their possible applications as second-order nonlinear optical materials.

Highly Regio- and Stereoselective DielsAlder Cycloaddition of Difluoro(methylene)cyclopropanes

Co-reporter:Xiao-Chun Hang;Qing-Yun Chen

European Journal of Organic Chemistry 2008 Volume 2008( Issue 6) pp:1101-1106

Publication Date(Web):

DOI:10.1002/ejoc.200700992

Abstract

The Diels–Alder reactions of difluoro(methylene)cyclopropanes (F₂MCPs) with cyclic dienes are described. These cycloaddition reactions exhibited complete regioselectivity and high endo-stereoselectivity. The obtained cycloadducts underwent a retro-Diels–Alder reaction to give the original dienophiles and dienes when heated, reflecting the reversible Diels–Alder reactivity of F₂MCPs.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Chiral N-heterocyclic carbene catalyzed annulation of α,β-unsaturated aldehydes with 1,3-dicarbonyls

Co-reporter:Zhi-Qiang Zhu, Xing-Liang Zheng, Ning-Fei Jiang, Xiaolong Wan and Ji-Chang Xiao

Chemical Communications 2011 - vol. 47(Issue 30) pp:NaN8672-8672

Publication Date(Web):2011/06/27

DOI:10.1039/C1CC12778K

Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts

Co-reporter:Cheng-Pan Zhang, Ji Cai, Chang-Bing Zhou, Xiao-Ping Wang, Xing Zheng, Yu-Cheng Gu and Ji-Chang Xiao

Chemical Communications 2011 - vol. 47(Issue 33) pp:NaN9518-9518

Publication Date(Web):2011/07/19

DOI:10.1039/C1CC13460D

Synthesis and reactions of the first fluoroalkylated Ni(II) N-confused porphyrins

Co-reporter:Hua-Wei Jiang, Qing-Yun Chen, Ji-Chang Xiao and Yu-Cheng Gu

Chemical Communications 2008(Issue 42) pp:

Publication Date(Web):

DOI:10.1039/B811831K

Progress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system

Co-reporter:Cheng-Pan Zhang, Qing-Yun Chen, Yong Guo, Ji-Chang Xiao and Yu-Cheng Gu

Chemical Society Reviews 2012 - vol. 41(Issue 12) pp:NaN4559-4559

Publication Date(Web):2012/04/17

DOI:10.1039/C2CS15352A

Novel low-melting salts with donor–acceptor substituents as targets for second-order nonlinear optical applications

Co-reporter:Zhi-Qiang Zhu, Shaoji Xiang, Qing-Yun Chen, Chaosen Chen, Zhuo Zeng, Yi-Ping Cui and Ji-Chang Xiao

Chemical Communications 2008(Issue 40) pp:NaN5018-5018

Publication Date(Web):2008/09/01

DOI:10.1039/B810671A

We synthesized several novel low-melting ionic salts with donor–acceptor substituents and investigated their possible applications as second-order nonlinear optical materials.

The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators and an unexpected intramolecular nucleophilic substitution reactionvia a proposed Ni(III) NCP intermediate

Co-reporter:Hua-Wei Jiang, Qing-Yun Chen, Ji-Chang Xiao and Yu-Cheng Gu

Chemical Communications 2009(Issue 25) pp:NaN3734-3734

Publication Date(Web):2009/05/15

DOI:10.1039/B904615A

Generation of the CF3 radical from trifluoromethylsulfonium triflate and its trifluoromethylation of styrenes

Co-reporter:Cheng-Pan Zhang, Zong-Ling Wang, Qing-Yun Chen, Chun-Tao Zhang, Yu-Cheng Gu and Ji-Chang Xiao

Chemical Communications 2011 - vol. 47(Issue 23) pp:NaN6634-6634

Publication Date(Web):2011/05/11

DOI:10.1039/C1CC11765C