Song Cao

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Name: 曹松; Cao, Song

Organization: East China University of Science and Technology (ECUST) , China

Department: School of Pharmacy

Title: Professor(PhD)

Chemicals
References

Cu-Catalyzed Stereoselective Borylation of gem-Difluoroalkenes with B2pin2

Co-reporter:Juan Zhang, Wenpeng Dai, Qingyun Liu, and Song Cao

Organic Letters June 16, 2017 Volume 19(Issue 12) pp:

Publication Date(Web):June 5, 2017

DOI:10.1021/acs.orglett.7b01430

A novel and efficient method for the synthesis of (Z)-fluorinated alkenylboronic acid pinacol esters via Cu-catalyzed stereoselective borylation of gem-difluoroalkenes using bis(pinacolato)diboron (B2pin2) as the boron source with the assistance of NaOtBu and Xantphos at room temperature was developed.

Direct copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with AgSCF3

Co-reporter:Wei Wu;Biyun Wang;Xinfei Ji

Organic Chemistry Frontiers 2017 vol. 4(Issue 7) pp:1299-1303

Publication Date(Web):2017/06/27

DOI:10.1039/C7QO00198C

A copper-catalyzed direct oxidative trifluoromethylthiolation of aryl boronic acids with AgSCF3 has been developed. This approach provides straightforward and efficient access to a variety of aryl trifluoromethyl sulfides from an easily prepared and stable nucleophilic trifluoromethylthiolation reagent AgSCF3, and readily available nucleophilic aryl boronic acids, thus avoiding the preparation of electrophilic trifluoromethylthiolating reagents in advance. Preliminary mechanistic experiments indicated that AgSCF3 served as both a source of SCF3 and an oxidant.

Synthesis of N,N-disubstituted 2-aminothiophenes by the cyclization of gem-difluoroalkenes with β-keto thioamides

Co-reporter:Xuxue Zhang;Mingsheng Wu;Juan Zhang

Organic & Biomolecular Chemistry 2017 vol. 15(Issue 11) pp:2436-2442

Publication Date(Web):2017/03/15

DOI:10.1039/C7OB00368D

A novel and effective method for the construction of highly functionalized aminothiophenes via the cyclization of gem-difluoroalkenes with β-keto tertiary thioamides is described. The reactions proceed smoothly with the assistance of K2CO3 under transition-metal-free conditions, affording a variety of valuable N,N-disubstituted 2-aminothiophenes in moderate to good yields.

Silver-Mediated anti-Markovnikov and Markovnikov-Selective Hydrotrifluoromethylthiolation of Terminal Alkynes

Co-reporter:Wei Wu, Wenpeng Dai, Xinfei Ji, and Song Cao

Organic Letters 2016 Volume 18(Issue 12) pp:2918-2921

Publication Date(Web):May 26, 2016

DOI:10.1021/acs.orglett.6b01286

The first example of direct hydrotrifluoromethylthiolation of terminal alkynes in the presence of AgSCF3 and K2S2O8 was established for the synthesis of a variety of vinyl trifluoromethyl thioethers. The anti-Markovnikov and Markovnikov adducts were obtained in moderate to good yields via two different reaction systems. Studies to probe the mechanism of the anti-Markovnikov addition reactions including the radical trapping experiments, kinetic isotope effect experiments, and deuterated experiments for determination of H-sources were conducted.

Sterically Controlled Cu-Catalyzed or Transition-Metal-Free Cross-Coupling of gem-Difluoroalkenes with Tertiary, Secondary, and Primary Alkyl Grignard Reagents

Co-reporter:Wenpeng Dai, Hongyan Shi, Xianghu Zhao, and Song Cao

Organic Letters 2016 Volume 18(Issue 17) pp:4284-4287

Publication Date(Web):August 19, 2016

DOI:10.1021/acs.orglett.6b02026

A robust copper-catalyzed or transition-metal-free cross-coupling of gem-difluoroalkenes with tertiary, secondary, and primary alkyl Grignard reagents has been developed. Remarkably, the tertiary and secondary alkylation of gem-difluoroalkenes proceeded very smoothly in the presence of 25 mol % of CuCN or under transition-metal-free conditions, affording the tertiary and secondary alkyl-substituted fluoroalkenes in good to excellent yields with excellent Z stereoselectivity.

Synthesis of Exocyclic Trisubstituted Alkenes via Nickel- Catalyzed Kumada-Type Cross-Coupling Reaction of gem- Difluoroalkenes with Di-Grignard Reagents

Co-reporter:Wenpeng Dai;Xuxue Zhang;Juan Zhang;Yingyin Lin

Advanced Synthesis & Catalysis 2016 Volume 358( Issue 2) pp:183-187

Publication Date(Web):

DOI:10.1002/adsc.201500889

Synthesis of fluorovinyl pyrazolyl (thio)ethers by the reaction of gem-difluoroalkenes with pyrazolin-5-ones (thiones)

Co-reporter:Tao Huang, Xianghu Zhao, Xinfei Ji, Wei Wu, Song Cao

Journal of Fluorine Chemistry 2016 Volume 182() pp:61-68

Publication Date(Web):February 2016

DOI:10.1016/j.jfluchem.2015.12.007

•An efficient method for the synthesis of fluorovinyl pyrazolyl (thio)ethers is reported.•The reaction of gem-difluoroalkenes with pyrazolin-5-ones (thiones) proceeds efficiently under mild conditions.•The addition of potassium tert-butoxide is essential for efficient conversion.A mild and efficient method for the preparation of fluorovinyl pyrazolyl ethers and thioethers by the reaction of gem-difluoroalkenes having aryl substituents with pyrazolin-5-ones and pyrazolin-5-thiones, respectively, in the presence of t-BuOK is described.

Frontispiece: Mild and Copper-Free Stereoselective Cyanation of gem-Difluoroalkenes by Using Benzyl Nitrile as a Cyanating Reagent

Co-reporter:Juan Zhang;Chengyuan Xu;Wei Wu ;Dr. Song Cao

Chemistry - A European Journal 2016 Volume 22( Issue 29) pp:

Publication Date(Web):

DOI:10.1002/chem.201682961

Mild and Copper-Free Stereoselective Cyanation of gem-Difluoroalkenes by Using Benzyl Nitrile as a Cyanating Reagent

Co-reporter:Juan Zhang;Chengyuan Xu;Wei Wu ;Dr. Song Cao

Chemistry - A European Journal 2016 Volume 22( Issue 29) pp:9902-9908

Publication Date(Web):

DOI:10.1002/chem.201601483

Abstract

A novel copper-free highly stereoselective cyanation of gem-difluoroalkenes by using benzyl nitrile as a cyanating reagent with the assistance of tBuOLi under air atmosphere at room temperature was developed. A variety of versatile fluorinated alkenyl nitriles were obtained. The proposed mechanism involved the C−H bond oxidation, C−CN bond cleavage, and then nucleophilic vinylic substitution (S_NV).

LDA-Mediated Synthesis of Triarylmethanes by Arylation of Diarylmethanes with Fluoroarenes at Room Temperature

Co-reporter:Xinfei Ji, Tao Huang, Wei Wu, Fang Liang, and Song Cao

Organic Letters 2015 Volume 17(Issue 20) pp:5096-5099

Publication Date(Web):October 6, 2015

DOI:10.1021/acs.orglett.5b02602

A practical and convenient approach for the secondary C(sp3)–H arylation of diarylmethanes with various fluoroarenes is described. The reaction proceeds smoothly in the presence of LDA (lithium diisopropylamide) at room temperature and affords triarylmethanes in moderate to high yields.

Copper-Catalyzed Coupling Cyclization of gem-Difluoroalkenes with Activated Methylene Carbonyl Compounds: Facile Domino Access to Polysubstituted Furans

Co-reporter:Xuxue Zhang, Wenpeng Dai, Wei Wu, and Song Cao

Organic Letters 2015 Volume 17(Issue 11) pp:2708-2711

Publication Date(Web):May 19, 2015

DOI:10.1021/acs.orglett.5b01123

A novel and efficient CuI-catalyzed synthesis of 2,3,5-trisubstituted furans was developed via coupling cyclization of gem-difluoroalkenes with active methylene carbonyl compounds such as 1,3-dicarbonyl compounds, acetoacetonitrile, and phenylsulfonylacetone with the assistance of a base. Commercial availability of substrates or reagents, good to high isolated yields, and excellent functional group compatibility make this transformation a powerful tool for the synthesis of various furans. A plausible mechanism involving the allenyl ketone is suggested.

Mild electrophilic trifluoromethylthiolation of ketones with trifluoromethanesulfanamide

Co-reporter:Wei Wu, Xuxue Zhang, Fang Liang and Song Cao

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 25) pp:6992-6999

Publication Date(Web):14 May 2015

DOI:10.1039/C5OB00960J

A straightforward and convenient approach for trifluoromethylthiolation of various acyclic and cyclic ketones with PhNHSCF3 is described. The reaction proceeds smoothly in the presence of acetyl chloride at room temperature and affords α-trifluoromethylthiolated ketones in fair to good yields.

Nickel-catalyzed Suzuki–Miyaura type cross-coupling reactions of (2,2-difluorovinyl)benzene derivatives with arylboronic acids

Co-reporter:Yang Xiong, Tao Huang, Xinfei Ji, Jingjing Wu and Song Cao

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 27) pp:7389-7392

Publication Date(Web):09 Jun 2015

DOI:10.1039/C5OB01016K

An unprecedented highly stereoselective example of nickel-catalyzed Suzuki–Miyaura type cross-coupling reactions of (2,2-difluorovinyl)benzene derivatives with arylboronic acids was developed. The reaction proceeded efficiently in the presence of 5 mol% NiCl2(PCy3)2 and K3PO4, affording the Z-fluorostyrene derivatives in good to high yields with excellent regioselectivity.

Synthesis of monofluoroalkenes through selective hydrodefluorination of gem-difluoroalkenes with Red-Al®

Co-reporter:Jingjing Wu, Juan Xiao, Wenpeng Dai and Song Cao

RSC Advances 2015 vol. 5(Issue 43) pp:34498-34501

Publication Date(Web):08 Apr 2015

DOI:10.1039/C5RA04221F

A novel and practical approach for the selective hydrodefluorination of gem-difluoroalkenes using Red-Al® as a reductant at room temperature in CH2Cl2 without any additional base and metal catalyst was reported. Various monofluoroalkenes were obtained in moderate to high yields with good E-selectivity.

Perfluorobutyl iodide-assisted direct cyanomethylation of azoles and phenols with acetonitrile

Co-reporter:Juan Zhang, Wei Wu, Xinfei Ji and Song Cao

RSC Advances 2015 vol. 5(Issue 26) pp:20562-20565

Publication Date(Web):10 Feb 2015

DOI:10.1039/C5RA02242H

A perfluorobutyl iodide-assisted transition-metal-free cyanomethylation of azoles and phenols with acetonitrile in the presence of NaH has been developed. The reaction proceeded smoothly under mild reaction conditions to give the cyanomethylated products in moderate to high yields. A mechanism involving the cyanomethyl radical through C–H bond cleavage in acetonitrile was proposed.

Metal-free one-pot sequential direct diarylation of pyrazolin-5-ones with diaryliodonium salts

Co-reporter:Tao Huang, Xinfei Ji, Wei Wu, Fang Liang and Song Cao

RSC Advances 2015 vol. 5(Issue 82) pp:66598-66601

Publication Date(Web):30 Jul 2015

DOI:10.1039/C5RA14368C

A novel and efficient one-pot sequential C4-diarylation of pyrazolin-5-ones with diaryliodonium salts in the absence of a metal catalyst was reported. A variety of C4-diarylated pyrazolin-5-one derivatives were obtained in good to high yields under mild conditions.

Synthesis of fluorovinyl aryl ethers by a three-component reaction of gem-difluoroalkenes with arylboronic acids and oxygen

Co-reporter:Mingjin Wang, Fang Liang, Yang Xiong and Song Cao

RSC Advances 2015 vol. 5(Issue 16) pp:11996-11999

Publication Date(Web):14 Jan 2015

DOI:10.1039/C4RA16468G

A novel and efficient three-component reaction for the synthesis of fluorovinyl aryl ethers from gem-difluoroalkenes, arylboronic acids and oxygen under metal-free conditions is described.

Base-mediated direct fluoroalkenylation of 2-phenyl-1,3,4-oxadiazole, benzothiazole and benzoxazole with gem-difluoroalkenes

Co-reporter:Xuxue Zhang, Yingyin Lin, Juan Zhang and Song Cao

RSC Advances 2015 vol. 5(Issue 11) pp:7905-7908

Publication Date(Web):22 Dec 2014

DOI:10.1039/C4RA13761B

Direct α-fluorovinylation of 2-phenyl-1,3,4-oxadiazole, benzothiazole and benzoxazole with gem-difluoroalkenes via nucleophilic vinylic substitution reaction (SNV) under the assistance of KHMDS or NaH at room temperature is described.

Mild and metal-free trifluoromethylation and pentafluoroethylation of gem-difluoroalkenes with TMSCF3 and TMSCF2CF3

Co-reporter:Guanyi Jin, Xuxue Zhang, Dan Fu, Wenpeng Dai, Song Cao

Tetrahedron 2015 Volume 71(Issue 41) pp:7892-7899

Publication Date(Web):14 October 2015

DOI:10.1016/j.tet.2015.08.016

A direct and efficient approach for the trifluoromethylation and pentafluoroethylation of 1,1-diaryl-2,2-difluoroethenes with TMSCF3 and TMSCF2CF3 in the presence of TBAF was developed. The reactions proceeded smoothly under mild reaction conditions to give the corresponding monotrifluoromethylated, bistrifluoromethylated, monopentafluoroethylated and bispentafluoroethylated products in fair to good yields, respectively, without the addition of metal catalyst.

Stereoselective synthesis of β-fluoroenyne by the reaction of gem-difluoroalkenes with terminal alkynes

Co-reporter:Guanyi Jin, Juan Zhang, Wei Wu, Song Cao

Journal of Fluorine Chemistry 2014 Volume 168() pp:240-246

Publication Date(Web):December 2014

DOI:10.1016/j.jfluchem.2014.10.010

•A new method for the stereoselective synthesis of conjugated β-fluoroenynes was reported.•The reactions of difluoroalkenes with terminal alkynes proceeded efficiently via SNV.•The addition of potassium orthophosphate is essential for efficient conversion.A mild and convenient method for the stereoselective synthesis of a series of conjugated β-fluoroenynes by the reaction of gem-difluoroalkenes with terminal alkynes with the assistance of n-butyllithium and K3PO4 is described.A mild and convenient method for the stereoselective synthesis of a series of conjugated β-fluoroenynes by the reaction of difluoroalkenes with terminal alkynes with the assistance of K3PO4 is described.

Synthesis of polyfluoroaryl-containing 1,2,3-triazoles by reaction of polyfluoroarenes, sodium azide and active methylene ketones/esters

Co-reporter:Jingjing Wu, Dan Fu, Song Cao

Journal of Fluorine Chemistry 2014 Volume 168() pp:230-235

Publication Date(Web):December 2014

DOI:10.1016/j.jfluchem.2014.10.009

•A one-pot three-component method for the synthesis of polyfluoroaryl-containing 1,4,5-trisubstituted 1,2,3-triazoles was reported.•The reactions proceeded under mild condition without any catalyst.•The addition of Na2CO3 is essential for efficient conversion.A series of polyfluoroaryl-containing 1,4,5-trisubstituted 1,2,3-triazoles were synthesized via a one-pot three-component reaction of polyfluoroarenes, sodium azide and active methylene ketones/esters by using CH3CN/H2O as solvent in the presence of Na2CO3 at room temperature.A series of polyfluoroaryl-containing 1,4,5-trisubstituted 1,2,3-triazoles were synthesized via a one-pot three-component reaction of polyfluoroarenes, sodium azide and active methylene ketones/esters by using CH3CN/H2O as solvent in the presence of Na2CO3 at room temperature.

Palladium- and Nickel-Catalyzed Kumada Cross-Coupling Reactions of gem-Difluoroalkenes and Monofluoroalkenes with Grignard Reagents

Co-reporter:Wenpeng Dai, Juan Xiao, Guanyi Jin, Jingjing Wu, and Song Cao

The Journal of Organic Chemistry 2014 Volume 79(Issue 21) pp:10537-10546

Publication Date(Web):October 18, 2014

DOI:10.1021/jo5022234

A novel Kumada–Tamao–Corriu cross-coupling reaction of gem-di- or monofluoroalkenes with Grignard reagents, with or without β-hydrogen atoms, in the presence of a catalytic amount of palladium- or nickel-based catalysts has been developed. The reaction is performed under mild conditions (room temperature or reflux in diethyl ether for 1–2 h) and leads to di-cross- or mono-cross-coupled products in good to high yields.

Copper-Free Direct C–H Trifluoromethylation of Acetanilides with Sodium Trifluoromethanesulfinate

Co-reporter:Mingxi Wu, Xinfei Ji, Wenpeng Dai, and Song Cao

The Journal of Organic Chemistry 2014 Volume 79(Issue 19) pp:8984-8989

Publication Date(Web):September 4, 2014

DOI:10.1021/jo501221h

A copper-free direct C–H ortho trifluoromethylation of electron-deficient 4-substituted acetanilides using Langlois reagent (NaSO2CF3) as the CF3 source in the presence of tert-butyl hydroperoxide (tBuOOH, TBHP) was developed.

Synthesis of N-(α-Fluorovinyl)azoles by the Reaction of Difluoroalkenes with Azoles

Co-reporter:Yang Xiong, Xuxue Zhang, Tao Huang, and Song Cao

The Journal of Organic Chemistry 2014 Volume 79(Issue 14) pp:6395-6402

Publication Date(Web):April 1, 2014

DOI:10.1021/jo5005845

A mild and versatile method for the construction of C–N bonds by the reaction of (2,2-difluorovinyl)arenes with various N–H-containing heterocycles in the presence of K3PO4 has been developed. The reaction proceeded efficiently at room temperature (25 °C) affording the (E)-N-α-fluorovinyl derivatives of azoles 3 in good to excellent yields with relatively high stereoselectivity.

Nickel-catalyzed N-heterocycle-directed cross-coupling of fluorinated arenes with organozinc reagents

Co-reporter:Sen-Han Xiao, Yang Xiong, Xu-Xue Zhang, Song Cao

Tetrahedron 2014 70(29) pp: 4405-4411

Publication Date(Web):

DOI:10.1016/j.tet.2014.04.052

Transition-Metal-Free Sonogashira-Type Cross-Coupling of Alkynes with Fluoroarenes

Co-reporter:Guanyi Jin, Xuxue Zhang, and Song Cao

Organic Letters 2013 Volume 15(Issue 12) pp:3114-3117

Publication Date(Web):June 11, 2013

DOI:10.1021/ol401317m

A novel, inexpensive, and efficient palladium-, copper-, ligand-, and amine-free Sonogashira-type cross-coupling reaction of terminal alkynes with unreactive aryl fluorides in the presence of sodium, sodium methoxide, and calcium hydroxide under the assistance of a Grignard reagent was developed. A plausible mechanism was also suggested.

NiCl2(PCy3)2-catalyzed hydrodefluorination of fluoroarenes with LiAl(O-t-Bu)3H

Co-reporter:Juan Xiao, Jingjing Wu, Wenwen Zhao, Song Cao

Journal of Fluorine Chemistry 2013 Volume 146() pp:76-79

Publication Date(Web):February 2013

DOI:10.1016/j.jfluchem.2012.12.002

A highly efficient and practical approach to the hydrodefluorination of CF bond in fluoroarenes in the presence of 5 mol% NiCl2(PCy3)2 with lithium tri-t-butoxyaluminium hydride (LiAl(O-t-Bu)3H) under mild conditions has been developed.Graphical abstractA highly efficient and practical NiCl2(PCy3)2-catalyzed hydrodefluorination of CF bond in fluoroarenes with lithium tri-t-butoxyaluminium hydride (LiAl(O-t-Bu)3H) was developed.Highlights► The activation of CF bonds. ► The hydrodefluorination of fluoarenes. ► A cheap, easy to handle reducing agent, lithium tri-t-butoxyaluminium hydride (LiAl(O-t-Bu)3H). ► Using 5 mol% NiCl2(PCy3)2 as catalyst.

Copper-mediated trifluoromethylation of 5-iodotriazole with (trifluoromethyl)trimethylsilane promoted by silver carbonate

Co-reporter:Dan Fu, Jian Zhang, Song Cao

Journal of Fluorine Chemistry 2013 Volume 156() pp:170-176

Publication Date(Web):December 2013

DOI:10.1016/j.jfluchem.2013.10.006

•A new method for the copper-mediated trifluoromethylation of 5-iodotriazole was reported.•The (trifluoromethyl)trimethylsilane was used as trifluoromethylating reagent.•The addition of silver carbonate is essential for efficient conversion.A novel and mild method for copper-mediated trifluoromethylation of 5-iodotriazole using (trifluoromethyl)trimethylsilane (Me3SiCF3) as trifluoromethylating reagent with the assistance of Ag2CO3 was developed.A novel and mild method for the copper-mediated trifluoromethylation of 5-iodotriazole using (trifluoromethyl)trimethylsilane as trifluoromethylating reagent with the assistance of Ag2CO3 was developed.

Copper(I)-Catalyzed Trifluoromethylation of Phthalic Anhydride Derivatives with (Trifluoromethyl)trimethylsilane

Co-reporter:Mingxi Wu;Mingjin Wang

Chinese Journal of Chemistry 2013 Volume 31( Issue 7) pp:945-949

Publication Date(Web):

DOI:10.1002/cjoc.201300357

Abstract

An efficient copper-catalyzed trifluoromethylation of substituted phthalic anhydrides using (trifluoromethyl) trimethylsilane (Me₃SiCF₃) as a nucleophilic trifluoromethylating reagent in the presence of 1,10-phenanthroline and KF, followed by quenching the reaction mixture with water has been developed. A possible mechanism was suggested.

Novel synthesis of 1,4,5-trisubstituted 1,2,3-triazoles via a one-pot three-component reaction of boronic acids, azide, and active methylene ketones

Co-reporter:Jian Zhang, Guanyi Jin, Senhan Xiao, Jingjing Wu, Song Cao

Tetrahedron 2013 69(10) pp: 2352-2356

Publication Date(Web):

DOI:10.1016/j.tet.2012.12.086

Noncatalytic Pyridyl-Directed Alkylation and Arylation Carbon–Fluorine Bond of Polyfluoroarenes with Grignard Reagents

Co-reporter:Yang Xiong, Jingjing Wu, Senhan Xiao, Juan Xiao, and Song Cao

The Journal of Organic Chemistry 2013 Volume 78(Issue 9) pp:4599-4603

Publication Date(Web):April 12, 2013

DOI:10.1021/jo400424d

Cross-coupling reaction of polyfluoroarenes with Grignard reagents via pyridine-directed cleavage of C–F bond in the absence of metal catalysts was developed. A possible mechanism was suggested.

Synthesis of unsymmetrical biaryl ethers through nickel-promoted coupling of polyfluoroarenes with arylboronic acids and oxygen

Co-reporter:Jian Zhang, Jingjing Wu, Yang Xiong and Song Cao

Chemical Communications 2012 vol. 48(Issue 68) pp:8553-8555

Publication Date(Web):06 Jul 2012

DOI:10.1039/C2CC33755J

Polyfluoro-substituted unsymmetrical biaryl ethers were synthesized via a novel Ni-catalyzed cross-coupling reaction of polyfluoroarenes with arylboronic acids and oxygen. The polyfluorinated arenes presumably captured the phenoxide intermediate efficiently, which made the oxygen-insertion proceed smoothly via the SNAr protocol. The 18O labeling experiment demonstrated that the oxygen introduced into unsymmetrical diaryl ether originated from very trace amounts of oxygen in the reaction system. A plausible mechanism was also suggested.

Highly Efficient Nickel(II) Chloride/Bis(tricyclohexylphosphine)nickel(II) Chloride-Cocatalyzed Hydrodefluorination of Fluoroarenes and Trifluorotoluenes with Superhydride

Co-reporter:Wenwen Zhao;Jingjing Wu

Advanced Synthesis & Catalysis 2012 Volume 354( Issue 4) pp:574-578

Publication Date(Web):

DOI:10.1002/adsc.201100783

Abstract

A simple and highly efficient approach for the hydrodefluorination of both fluoroarenes and trifluorotoluenes in the presence of lithium triethylborohydride using a catalytic amount of nickel(II) chloride (NiCl₂, 2 mol%) combined with a catalytic amount of bis(tricyclohexylphosphine)nickel(II) chloride [NiCl₂(PCy₃)₂, 2 mol%] as cocatalyst has been developed.

One-Pot, Three-Component Synthesis of 1,4,5-Trisubstituted 1,2,3-Triazoles Starting from Primary Alcohols

Co-reporter:Guanyi Jin;Jian Zhang;Dan Fu;Jingjing Wu

European Journal of Organic Chemistry 2012 Volume 2012( Issue 28) pp:5446-5449

Publication Date(Web):

DOI:10.1002/ejoc.201200830

Abstract

A novel, one-pot, three-component approach for the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles through the cycloaddition of a wide range of primary alcohols with sodium azide and active methylene ketones in the presence of N-(p-toluenesulfonyl)imidazole, tetrabutylammonium iodide, and triethylamine in DMF/DMSO has been developed.

Synthesis of Difluoromethyl-Containing -Acyloxycarboxamide Derivatives through a Passerini Reaction and Desulfonylation

Co-reporter:Jingjing Wu;Wenwen Zhao

European Journal of Organic Chemistry 2012 Volume 2012( Issue 7) pp:1380-1387

Publication Date(Web):

DOI:10.1002/ejoc.201101518

Abstract

A series of difluoromethyl-containing α-acyloxycarboxamide derivatives were synthesized through a Passerini reaction of acids, aldehydes, and phenylsulfanyl-protected difluorinated isocyanide followed by meta-chloroperoxybenzoic acid mediated oxidation and the removal of the phenylsulfonyl protecting group. The unexpected formation of deacylation products from the reaction between the Passerini products and Bu₃SnH/azobis(isobutyronitrile) was also reported.

One-pot Three Component Synthesis of Polyfluoroarylated Arylacetates via VNSAr-SNAr Reaction

Co-reporter:Yang Xiong;Jingjing Wu;Senhan Xiao

Chinese Journal of Chemistry 2012 Volume 30( Issue 12) pp:2747-2751

Publication Date(Web):

DOI:10.1002/cjoc.201201044

Abstract

A series of 2-polyfluoroaryl arylacetates were synthesized by a one-pot three-component VNS_Ar-S_NAr reaction of polyfluoroarenes, ethyl 2-chloropropionate, and ortho-substituted nitrobenzenes.

Synthesis and Insecticidal Activities of Novel Analogues of Flubendiamide Containing a Hexafluoroisopropanol Moiety

Co-reporter:Mingxi Wu;Wenwen Zhao;Guanyi Jin;Qingchun Huang

Chinese Journal of Chemistry 2012 Volume 30( Issue 6) pp:1310-1314

Publication Date(Web):

DOI:10.1002/cjoc.201200215

Abstract

Ten novel analogues of flubendiamide containing a hexafluoroisopropanol moiety were designed and synthesized. Their insecticidal activities against armyworm (Pseudaletia separata Walker) were examined and compared with the commercial product flubendiamide. Compound 7b showed nearly the same insecticidal activity as flubendiamide against armyworm.

Oxidation of benzylic methylenes to ketones with Oxone–KBr in aqueous acetonitrile under transition metal free conditions

Co-reporter:Lixia Yin, Jingjing Wu, Juan Xiao, Song Cao

Tetrahedron Letters 2012 Volume 53(Issue 33) pp:4418-4421

Publication Date(Web):15 August 2012

DOI:10.1016/j.tetlet.2012.06.036

A green and highly efficient protocol for the oxidation of benzylic methylenes to their corresponding ketones with a combination of Oxone and KBr in aqueous acetonitrile is developed. The H218O labeling experiment demonstrated that the oxygen introduced into ketone originated from water. A plausible mechanism was also suggested.

Novel Synthesis of Difluoromethyl-Containing 1,4-Disubstituted 1,2,3-Triazoles via a ClickMulticomponent Reaction and Desulfanylation Strategy

Co-reporter:Jian Zhang;Jingjing Wu;Li Shen;Guanyi Jin

Advanced Synthesis & Catalysis 2011 Volume 353( Issue 4) pp:580-584

Publication Date(Web):

DOI:10.1002/adsc.201000791

Abstract

Fourteen difluoromethyl-containing 1,4-disubstituted 1,2,3-triazoles were synthesized via a novel copper-catalyzed click-multicomponent reaction of 2,2-difluoro-2-phenylsulfanylethanol, sodium azide and terminal alkynes in the presence of N- (p-toluenesulfonyl)imidazole, tetrabutylammonium iodide and triethylamine, followed by reductive cleavage of the phenylsulfanyl group using tributyltin hydride and azobisisobutyronitrile.

Synthesis of Novel gem-Difluoromethylene-containing 1,2,3-Triazoles via Click Reaction

Co-reporter:Wenwen Zhao;Hui Li;Jian Zhang

Chinese Journal of Chemistry 2011 Volume 29( Issue 12) pp:2763-2768

Publication Date(Web):

DOI:10.1002/cjoc.201100311

Abstract

Seventeen novel gem-difluoromethylene-containing 1,2,3-triazoles were synthesized by the click reaction of ethyl 2-azido-2,2-difluoroacetate and terminal alkynes in the presence of 10 mol% CuI.

One-pot synthesis of difluoromethyl-containing dihydropyrimidinones catalyzed by Yb(PFO)3 under solvent and dehydrating agent free conditions

Co-reporter:Mingxi Wu, Jinlong Yu, Wenwen Zhao, Jingjing Wu, Song Cao

Journal of Fluorine Chemistry 2011 Volume 132(Issue 3) pp:155-159

Publication Date(Web):March 2011

DOI:10.1016/j.jfluchem.2010.12.010

The difluoromethyl-containing Biginelli dihydropyrimidinone derivatives were synthesized by a one-pot cyclocondensation of ethyl 4,4-difluoroacetoacetate, urea, and a variety of aldehydes in the presence of 5 mol% ytterbium perfluorooctanoate [Yb(PFO)3] under solvent and dehydrating agent free conditions. The comparison of reaction conditions and products was made among the different 1,3-dicarbonyl substrates (ethyl acetoacetate, ethyl 4,4-difluoroacetoacetate and ethyl 4,4,4-trifluoroacetoacetate) for the Biginelli reaction.Graphical abstractThe difluoromethyl-containing dihydropyrimidinone derivatives were synthesized by cyclocondensation of ethyl 4,4-difluoroacetoacetate, urea, and aldehydes in the presence of ytterbium perfluorooctanoate under solvent free conditions.Research highlights▶ Synthesis of difluoromethyl-containing dihydropyrimidinones. ▶ Biginelli reaction in the presence of Yb(PFO)3 under solvent-free conditions. ▶ Ethyl 4,4-difluoroacetoacetate used as substrate. ▶ Comparison of reaction conditions and products was made among three 1,3-dicarbonyl substrates.

ZnCl2-catalyzed hydrodefluorination of gem-difluoromethylene derivatives with lithium aluminum hydride

Co-reporter:Jianhang Cheng, Jingjing Wu, Song Cao

Tetrahedron Letters 2011 Volume 52(Issue 27) pp:3481-3484

Publication Date(Web):6 July 2011

DOI:10.1016/j.tetlet.2011.04.114

Hydrodefluorination of gem-difluoromethylene derivatives with lithium aluminum hydride in the presence of a catalytic amount of ZnCl2 in good to high yields was described. A possible mechanism is also suggested.Hydrodefluorination of gem-difluoromethylene derivatives with lithium aluminum hydride in the presence of a catalytic amount of ZnCl2 in good to high yields was described. A possible mechanism is also suggested.

Non-catalytic conversion of C–F bonds of gem-difluoromethylene derivatives to C–H bonds with lithium aluminum hydride under room temperature

Co-reporter:Jing-Jing Wu, Jian-Hang Cheng, Jian Zhang, Li Shen, Xu-Hong Qian, Song Cao

Tetrahedron 2011 67(2) pp: 285-288

Publication Date(Web):

DOI:10.1016/j.tet.2010.11.052

Nickel-Catalyzed Hydrodefluorination of Fluoroarenes and Trifluorotoluenes with Superhydride (Lithium Triethylborohydride)

Co-reporter:Jingjing Wu ; Song Cao

ChemCatChem 2011 Volume 3( Issue 10) pp:1582-1586

Publication Date(Web):

DOI:10.1002/cctc.201100083

A general strategy for construction of a difluoromethyl compound library and its application in synthesis of pseudopeptides bearing a terminal difluoromethyl group

Co-reporter:Jingjing Wu, Song Cao, Nianjin Liu, Li Shen, Jinlong Yu, Jian Zhang, Hui Li and Xuhong Qian

Organic & Biomolecular Chemistry 2010 vol. 8(Issue 10) pp:2386-2391

Publication Date(Web):17 Mar 2010

DOI:10.1039/C000835D

We describe the development of a novel synthesis strategy that uses common reaction conditions to transform a collection of simple building blocks into complex molecules bearing a terminal difluoromethyl group. The core of this approach is the conscious design and synthesis of new difluorinated building blocks which contain inactive and reactive groups on each side of the CF2 group. The strategy is illustrated by application to the synthesis of CF2H-bearing pseudopeptides via Ugi reaction.

Synthesis and Insecticidal Activity of Heptafluoroisopropyl-Containing Benzoylphenylurea Structures†

Co-reporter:Jian Zhang, Xiuhong Tang, Isaac Ishaaya, Song Cao, Jingjing Wu, Jinlong Yu, Hui Li and Xuhong Qian

Journal of Agricultural and Food Chemistry 2010 Volume 58(Issue 5) pp:2736-2740

Publication Date(Web):December 16, 2009

DOI:10.1021/jf9025508

Fourteen novel heptafluoroisopropyl-containing benzoylphenylureas were designed and synthesized. Their insecticidal activities against armyworm (Pseudaletia separata Walker) were examined and compared with the commercial product diflubenzuron. Three compounds (IIi, IIj, and IIk) showed excellent insecticidal effect, and their activity resembled that of diflubenzuron. Compound IIi also showed nearly the same insecticidal activity as novaluron on African cotton leafworm (Spodoptera littoralis). Furthermore, results from a field trial indicated that 5% EC IIi exhibited similar efficacy in comparison with chlorfluazuron and hexaflumuron against imported cabbage worm (Pieris rapae L.) and diamondback moth (Plutella xylostella), respectively.

K2CO3-assisted one-pot sequential synthesis of 2-trifluoromethyl-6-difluoromethylpyridine-3,5-dicarboxylates under solvent-free conditions

Co-reporter:Li Shen, Song Cao, Jingjing Wu, Hui Li, Jian Zhang, Mingxi Wu, Xuhong Qian

Tetrahedron Letters 2010 Volume 51(Issue 37) pp:4866-4869

Publication Date(Web):15 September 2010

DOI:10.1016/j.tetlet.2010.07.041

A novel synthesis of 2-trifluoromethyl-6-difluoromethylpyridine-3,5-dicarboxylates by three-component reaction of ethyl trifluoroacetoacetate, aldehydes, and ammonium acetate in the presence of K2CO3 under solvent-free conditions via sequential Hantzsch reaction/dehydration/dehydrofluorination in a one-pot process was described.A novel synthesis of 2-trifluoromethyl-6-difluoromethylpyridine-3,5-dicarboxylates via K2CO3-assisted one-pot sequential Hantzsch reaction/dehydration/dehydrofluorination under solvent-free conditions was described.

A mild and efficient synthesis of monofluorinated α-lactam pseudopeptides via a novel dehydrofluorination of Ugi products

Co-reporter:Nianjin Liu;Jingjing Wu;Li Shen;Jinlong Yu;Jian Zhang

Molecular Diversity 2010 Volume 14( Issue 3) pp:501-506

Publication Date(Web):2010/08/01

DOI:10.1007/s11030-009-9209-x

Six novel monofluorinated α-lactam pseudopeptide derivatives were synthesized via Ugi reaction using gem-difluoromethylene-containing isocyanide as a key component, followed by dehydrofluorination of Ugi products in one pot without additional base.

An efficient three-component domino synthesis of difluoromethyl-containing 1,4-dihydropyridines under solvent and catalyst free conditions

Co-reporter:Hui Li;JinLong Yu;Li Shen;MingXi Wu;JianHang Cheng

Science China Chemistry 2010 Volume 53( Issue 7) pp:1509-1513

Publication Date(Web):2010 July

DOI:10.1007/s11426-010-4005-0

The difluoromethyl-containing Hantzsch 1,4-dihydropyridines were synthesized in good yields by a one-pot cyclocondensation of ethyl difluoroacetoacetate (EDFAA), a variety of aromatic aldehydes and ammonium acetate under solvent and catalyst free conditions. The comparison of reaction conditions and products was made among the different 1,3-carbonyl substrates (ethyl acetoacetate, ethyl difluoroacetoacetate and ethyl trifluoroacetoacetate) for the Hantzsch reaction.

New gem-difluoromethylene-containing isocyanide as a useful building block for the synthesis of difluorinated pseudopeptides via Ugi reaction

Co-reporter:Nianjin Liu, Song Cao, Li Shen, Jingjing Wu, Jinlong Yu, Jian Zhang, Hui Li, Xuhong Qian

Tetrahedron Letters 2009 50(17) pp: 1982-1985

Publication Date(Web):

DOI:10.1016/j.tetlet.2009.02.056

One-pot three component synthesis of heteroarylated arylacetates viaVNSAr-SN reaction using N-methylpyrrolidone as general solvent

Co-reporter:Song Cao, Jingjing Wu, Lina Li, Longjie Zhu, Jian Zhang, Jinlong Yu and Xuhong Qian

Organic & Biomolecular Chemistry 2008 vol. 6(Issue 7) pp:1293-1297

Publication Date(Web):27 Feb 2008

DOI:10.1039/B719185E

An efficient three component one-pot method was developed to assemble 2-heteroaryl-2-aryl acetates viaVNSAr-SNAr and VNSAr-SN reaction by using N-methylpyrrolidone (NMP) as general solvent.

Synthesis of thiohydantoins under one-pot three-component solvent-free conditions

Co-reporter:Song Cao;Longjie Zhu;Chuanmeng Zhao

Monatshefte für Chemie - Chemical Monthly 2008 Volume 139( Issue 8) pp:

Publication Date(Web):2008 August

DOI:10.1007/s00706-007-0842-8

A direct and efficient one-pot three-component synthesis protocol was developed for the synthesis of thiohydantoins from readily and widely available substrates (isothiocyanates, ethyl chloroacetate, and amines) employing solvent-free conditions.

n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature

Co-reporter:Yingyin Lin, Meng Li, Xinfei Ji, Jingjing Wu, Song Cao

Tetrahedron (16 March 2017) Volume 73(Issue 11) pp:1466-1472

Publication Date(Web):16 March 2017

DOI:10.1016/j.tet.2017.01.050

Recent advances in the synthesis and CF functionalization of gem-difluoroalkenes

Co-reporter:Xuxue Zhang, Song Cao

Tetrahedron Letters (1 February 2017) Volume 58(Issue 5) pp:

Publication Date(Web):1 February 2017

DOI:10.1016/j.tetlet.2016.12.054

•The gem-difluoroalkenes are versatile fluorinated building blocks.•The new and useful reactions involve the cleavage of CF bond in gem-difluoroalkenes.•The recent advances in the synthesis and reaction chemistry of gem-difluoroalkenes are reviewed.The gem-difluoroalkenes and related compounds have gained much attention from the organic synthetic community due to their widespread applications as versatile fluorinated building blocks for the synthesis of pharmaceuticals, agrochemicals and functional materials. In the past two decades, significant progress has been made to the development of efficient methods for the construction of gem-difluoroalkenes and useful reactions involving the cleavage of CF bond in gem-difluoroalkenes. In this Digest review, these advances in the synthesis and reaction chemistry of gem-difluoroalkenes are summarized, with special emphasis placed on novel synthetic applications of them in recent ten years.Download high-res image (88KB)Download full-size image

One-pot three component synthesis of heteroarylated arylacetates viaVNSAr-SN reaction using N-methylpyrrolidone as general solvent

Co-reporter:Song Cao, Jingjing Wu, Lina Li, Longjie Zhu, Jian Zhang, Jinlong Yu and Xuhong Qian

Organic & Biomolecular Chemistry 2008 - vol. 6(Issue 7) pp:NaN1297-1297

Publication Date(Web):2008/02/27

DOI:10.1039/B719185E

An efficient three component one-pot method was developed to assemble 2-heteroaryl-2-aryl acetates viaVNSAr-SNAr and VNSAr-SN reaction by using N-methylpyrrolidone (NMP) as general solvent.

Synthesis of unsymmetrical biaryl ethers through nickel-promoted coupling of polyfluoroarenes with arylboronic acids and oxygen

Co-reporter:Jian Zhang, Jingjing Wu, Yang Xiong and Song Cao

Chemical Communications 2012 - vol. 48(Issue 68) pp:NaN8555-8555

Publication Date(Web):2012/07/06

DOI:10.1039/C2CC33755J

Synthesis of N,N-disubstituted 2-aminothiophenes by the cyclization of gem-difluoroalkenes with β-keto thioamides

Co-reporter:Xuxue Zhang, Mingsheng Wu, Juan Zhang and Song Cao

Organic & Biomolecular Chemistry 2017 - vol. 15(Issue 11) pp:NaN2442-2442

Publication Date(Web):2017/02/24

DOI:10.1039/C7OB00368D

LDA-mediated synthesis of ortho-cyanated diarylmethanes by reaction of fluoroarene with arylacetonitrile at room temperature

Co-reporter:Fang Liang, Xinfei Ji, Juan Zhang and Song Cao

Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 11) pp:NaN1429-1429

Publication Date(Web):2016/08/26

DOI:10.1039/C6QO00363J

An efficient and facile method for the synthesis of ortho-cyanated diarylmethane by reaction of fluoroarene with arylacetonitrile in the presence of LDA (lithium diisopropylamide) at room temperature was developed. The reaction of arylacetonitrile with electron-rich fluoroarene involves the formation of an aryne intermediate.

Direct copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with AgSCF3

Co-reporter:Wei Wu;Biyun Wang;Xinfei Ji

Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 7) pp:

Publication Date(Web):2017/06/27

DOI:10.1039/C7QO00198C

Nickel-catalyzed Suzuki–Miyaura type cross-coupling reactions of (2,2-difluorovinyl)benzene derivatives with arylboronic acids

Co-reporter:Yang Xiong, Tao Huang, Xinfei Ji, Jingjing Wu and Song Cao

Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 27) pp:NaN7392-7392

Publication Date(Web):2015/06/09

DOI:10.1039/C5OB01016K

A general strategy for construction of a difluoromethyl compound library and its application in synthesis of pseudopeptides bearing a terminal difluoromethyl group

Co-reporter:Jingjing Wu, Song Cao, Nianjin Liu, Li Shen, Jinlong Yu, Jian Zhang, Hui Li and Xuhong Qian