Guosheng Liu

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Name: 刘国生; Liu, GuoSheng

Organization: Chinese Academy of Sciences , China

Department: Shanghai Institute of Organic Chemistry

Title: Researcher(PhD)

TOPICS

Organic Chemistry

Fluorination Trifluoromethylation Cyanation allene

Chemicals
References

Palladium-Catalyzed Intermolecular Azidocarbonylation of Alkenes via a Cooperative Strategy

Co-reporter:Ming Li, Feng Yu, Pinhong Chen, and Guosheng Liu

The Journal of Organic Chemistry November 17, 2017 Volume 82(Issue 22) pp:11682-11682

Publication Date(Web):August 24, 2017

DOI:10.1021/acs.joc.7b01812

A novel intermolecular β-azidocarbonylation reaction of alkenes has been developed in which a combination of iodine(III)-mediated alkene activation and palladium-catalyzed carbonylation was demonstrated as an efficient strategy for the difunctionalization of alkenes. A variety of β-azido carboxylic esters were obtained from mono- and 1,1-disubstituted terminal alkenes with excellent regioselectivities. In addition, the introduced azido group can be reduced to an amine group, providing a facile access to β-amino acid derivatives from simple olefins.

Asymmetric Copper-Catalyzed Intermolecular Aminoarylation of Styrenes: Efficient Access to Optical 2,2-Diarylethylamines

Co-reporter:Dinghai Wang, Lianqian Wu, Fei Wang, Xiaolong Wan, Pinhong Chen, Zhenyang Lin, and Guosheng Liu

Journal of the American Chemical Society May 24, 2017 Volume 139(Issue 20) pp:6811-6811

Publication Date(Web):May 4, 2017

DOI:10.1021/jacs.7b02455

We have developed a copper-catalyzed enantioselective intermolecular aminoarylation of alkenes using a novel N-fluoro-N-alkylsulfonamide as the amine reagent, which could react with the Cu(I) catalyst to release a related amino radical. After addition to styrene, the generated benzylic radical could couple with a chiral L*CuIIAr complex to achieve enantioselective arylation. Various optical 2,2-diarylethylamines were efficiently synthesized from simple styrenes with high enantioselectivity, and these products can serve as valuable synthons toward bioactive molecules’ synthesis.

Copper-Catalyzed Arylation of Benzylic C–H bonds with Alkylarenes as the Limiting Reagents

Co-reporter:Wen Zhang, Pinhong Chen, and Guosheng Liu

Journal of the American Chemical Society June 14, 2017 Volume 139(Issue 23) pp:7709-7709

Publication Date(Web):May 31, 2017

DOI:10.1021/jacs.7b03781

A novel copper-catalyzed arylation of benzylic C–H bonds with nucleophilic arylboronic acids has been developed that provides an efficient way to synthesize various 1,1-diarylalkanes with a broad substrate scope and excellent functional group compatibility. The reactions occur at room temperature using alkylarenes as the limiting reagents, which allows access to the arylation of the more valuable and complex bioactive compounds.

Palladium-Catalyzed Intermolecular Oxidative Diazidation of Alkenes

Co-reporter:Haihui Peng;Zheliang Yuan;Pinhong Chen

Chinese Journal of Chemistry 2017 Volume 35(Issue 6) pp:876-880

Publication Date(Web):2017/06/01

DOI:10.1002/cjoc.201600834

AbstractA palladium-catalyzed oxidative vicinal diazidation of alkenes has been developed, in which TMSN3 was used as azide source. Both styrenes and unactivated alkenes are suitable for this reaction. And trans-alkyldiazides were obtained as major products from cyclic alkenes with moderate to good diastereoselectivities. This reaction afforded an efficient way for the synthesis of useful 1,2-diamines after hydrogenation.

Intermolecular Palladium-Catalyzed Oxidative Fluorocarbonylation of Unactivated Alkenes: Efficient Access to β-Fluorocarboxylic Esters

Co-reporter:Xiaoxu Qi;Dr. Feng Yu;Dr. Pinhong Chen; Dr. Guosheng Liu

Angewandte Chemie International Edition 2017 Volume 56(Issue 41) pp:12692-12696

Publication Date(Web):2017/10/02

DOI:10.1002/anie.201706401

AbstractA novel palladium-catalyzed intermolecular oxidative fluorocarbonylation of alkenes has been developed, in which employment of a cooperative process with electrophilic ArIF2-meidated alkenes activation and palladium-catalyzed carbonylation is crucial for the successful catalytic transformation. The current transformation presents the first convenient method to generate β-fluorinated carboxylic acid derivatives under mild reaction conditions from simple alkenes with excellent regioselectivity.

Enantioselective Palladium(II)-Catalyzed Intramolecular Aminoarylation of Alkenes by Dual N−H and Aryl C−H Bond Cleavage

Co-reporter:Wen Zhang;Dr. Pinhong Chen; Dr. Guosheng Liu

Angewandte Chemie International Edition 2017 Volume 56(Issue 19) pp:5336-5340

Publication Date(Web):2017/05/02

DOI:10.1002/anie.201700889

AbstractAn asymmetric palladium-catalyzed intramolecular oxidative aminoarylation of alkenes has been developed with quinoline–oxazoline chiral ligands and Ag2CO3 as the oxidant. Various indolines containing a quaternary stereogenic center were synthesized in high yield with excellent enantioselectivity. Preliminary mechanistic studies suggest that the addition of a catalytic amount of phenylglyoxylic acid significantly accelerates the reaction and slightly enhances the enantioselectivity.

Palladium(II)-Catalyzed Oxidative Difunctionalization of Alkenes: Bond Forming at a High-Valent Palladium Center

Co-reporter:Guoyin Yin, Xin Mu, and Guosheng Liu

Accounts of Chemical Research 2016 Volume 49(Issue 11) pp:2413

Publication Date(Web):October 14, 2016

DOI:10.1021/acs.accounts.6b00328

Difunctionalization of alkenes to incorporate two functional groups across a double bond has emerged as a powerful transformation to greatly increase molecular complexity in organic synthesis with improved efficiency. Historically, palladium-catalyzed difunctionalization of alkenes has suffered from difficulties with introducing a second functional group through reductive elimination of a Pd(II) intermediate and competing β-hydride elimination reactions. To overcome these challenges, one strategy involves utilizing a steric bulky ligand to promote the reductive elimination steps from the Pd(II) center and impeding the β-hydride elimination reactions, which are beyond the scope of this Account. Alternatively, strong oxidants have been utilized to generate high-valent palladium species, which are prone to undergo reductive elimination to form a second C–X bond. This new strategy has been extensively applied to explore the difunctionalization of alkenes with enriched functional group diversity over the past decade.In this Account, we discuss our exploration and application of a “high-valent palladium strategy” for the synthesis of fluorine-containing organic molecules that are typically inaccessible from other methods. These studies were focused on the difunctionalization of alkenes that was initiated by nucleopalladation to form the alkyl C–Pd(II) species in high exo/endo regioselectivity. In the presence of nucleophilic fluorine-containing reagents (e.g., AgF, TMSCF3, and AgOCF3) and strong oxidants (hypervalent iodine and electrophilic fluorinating reagents), the in situ generated fluorine-containing high-valent Pd(IV) intermediates undergo reductive elimination to provide the corresponding alkyl C–F, C–CF3, and C–OCF3 bonds. Using these methods, we synthesized a variety of heterocycles containing fluorine, trifluoromethyl, and trifluoromethoxyl moieties from alkene substrates under mild reaction conditions. Besides hypervalent iodine reagents and electrophilic fluorinating reagents, our group has demonstrated that hydrogen peroxide, which is an environmentally friendly oxidant, can oxidize alkyl C–Pd(II) species to form high-valent alkyl C–Pd intermediates, and based on this observation, several catalytic difunctionalizations of alkenes, such as aminochlorination, aminoacetoxylation, and aminohydroxylation reactions, have been successfully developed. In addition, water was the only waste derived from the oxidant. All of these studies provide attractive methods for the stereoselective introduction of C–N and C–O bonds across double bonds via high-valent palladium intermediates. To gain a deeper understanding of this “high-valent palladium strategy”, systematic mechanistic studies were performed to illustrate the stereochemistry of aminopalladation and reductive elimination. These results are summarized in the final section and serve as a guide for further exploration of novel alkene transformation as well as in other areas, such as Pd-catalyzed C–H bond functionalization reactions.

Enantioselective Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes via Radical Process

Co-reporter:Fei Wang, Dinghai Wang, Xiaolong Wan, Lianqian Wu, Pinhong Chen, and Guosheng Liu

Journal of the American Chemical Society 2016 Volume 138(Issue 48) pp:15547-15550

Publication Date(Web):November 14, 2016

DOI:10.1021/jacs.6b10468

A novel enantioselective copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which a variety of CF3-containing alkylnitriles are furnished with excellent enantiomeric excess. Preliminary mechanistic studies revealed (1) the reaction was initiated by a SET process between activated Togni’s CF3+ reagent and a Cu(I) catalyst; (2) the released CF3 radical readily added to styrene to provide a benzylic radical, which was then trapped by a chiral Cu(II) cyanide species to deliver the desired alkylnitriles; (3) a low concentration of the CN anion was crucial to obtain high enantioselectivity.

Pd(II)-Catalyzed Aminofluorination of Alkenes in Total Synthesis 6-(R)-Fluoroswainsonine and 5-(R)-Fluorofebrifugine

Co-reporter:Liang Wu, Pinhong Chen, and Guosheng Liu

Organic Letters 2016 Volume 18(Issue 5) pp:960-963

Publication Date(Web):February 16, 2016

DOI:10.1021/acs.orglett.6b00030

The total syntheses of two fluorinated alkaloids, 6-(R)-fluoroswainsonine and 5-(R)-fluorofebrifugine, are described. Both encompass (4aS,7R,8aR)-7-fluoro-5-tosylhexahydro-4H-[1,3]dioxino[5,4-b]pyridine as a key synthon which is obtained through a further optimized palladium-catalyzed aminofluorination of alkenes with high diastereoselectivity. 6-(R)-Fluoroswainsonine is synthesized from the key synthon in 14 steps, and 5-(R)-fluorofebrifugine requires a sequential 15-step transformation.

Co-reporter:Fei Wang;Dinghai Wang;Scott D. McCann;Wen Zhang;Pinhong Chen;Shannon S. Stahl

Science 2016 Volume 353(Issue 6303) pp:

Publication Date(Web):

DOI:10.1126/science.aaf7783

Abstract

Direct methods for stereoselective functionalization of sp³-hybridized carbon–hydrogen [C(sp³)–H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp³)–CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.

Mechanistic Investigation on the Silver-Catalyzed Oxidative Intramolecular Aminofluorination of Alkynes

Co-reporter:Tao Xu, Yichen Wu, Zheliang Yuan, Hairong Guan, and Guosheng Liu

Organometallics 2016 Volume 35(Issue 10) pp:1347-1349

Publication Date(Web):March 3, 2016

DOI:10.1021/acs.organomet.6b00054

In this work, a mechanistic study of silver-catalyzed oxidative aminofluorination of alkynyl-imine has been carried out. Kinetic data support a reaction pathway involving fast amination of alkyne to mesoionic carbene silver complexes (MIC)nAg(I) (n = 1 or 2). The rate-determining step of the reaction is the fluorination of the Ag species supported by a single MIC.

Palladium-Catalyzed Intramolecular Aminotrifluoromethoxylation of Alkenes

Co-reporter:Chaohuang Chen; Pinhong Chen

Journal of the American Chemical Society 2015 Volume 137(Issue 50) pp:15648-15651

Publication Date(Web):December 4, 2015

DOI:10.1021/jacs.5b10971

The first catalytic trifluoromethoxylation of unactivated alkenes has been developed, in which Pd(CH3CN)2Cl2 was used as catalyst, AgOCF3 as trifluoromethoxide source, and Selectfluor-BF4 as oxidant. A variety of 3-OCF3 substituted piperidines were selectively obtained in good yields. Direct evidence was provided to address the facile reductive elimination of PdIV–OCF3 complex to form sp3 C–OCF3 bond.

Highly Selective Pd-Catalyzed Intermolecular Fluorosulfonylation of Styrenes

Co-reporter:Zheliang Yuan; Hao-Yang Wang; Xin Mu; Pinhong Chen; Yin-Long Guo

Journal of the American Chemical Society 2015 Volume 137(Issue 7) pp:2468-2471

Publication Date(Web):February 4, 2015

DOI:10.1021/ja5131676

A novel Pd-catalyzed intermolecular regio- and diastereoselective fluorosulfonylation of styrenes has been developed under mild conditions. This reaction exhibits a wide range of functional-group tolerance in styrenes and arylsulfinic acids to afford various β-fluoro sulfones. Preliminary mechanistic study reveals an unusual mechanism, in which a high-valent L2PdIIIF species side-selectively reacts with a benzylic carbon radical to deliver a C–F bond. This pathway is distinct from a previously reported radical fluorination reaction.

Palladium-Catalyzed Intermolecular Aminocarbonylation of Alkenes: Efficient Access of β-Amino Acid Derivatives

Co-reporter:Jiashun Cheng; Xiaoxu Qi; Ming Li; Pinhong Chen

Journal of the American Chemical Society 2015 Volume 137(Issue 7) pp:2480-2483

Publication Date(Web):February 12, 2015

DOI:10.1021/jacs.5b00719

A novel palladium-catalyzed intermolecular aminocarbonylation of alkenes has been developed in which the employment of hypervalent iodine reagent can accelerate the intermolecular aminopalladation, which thus provides the successful catalytic transformation. The current transformation presents one of the most convenient methods to generate β-amino acid derivatives from simple alkenes.

Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination

Co-reporter:Qilun Liu, Zheliang Yuan, Hao-yang Wang, Yang Li, Yichen Wu, Tao Xu, Xuebing Leng, Pinhong Chen, Yin-long Guo, Zhenyang Lin, and Guosheng Liu

ACS Catalysis 2015 Volume 5(Issue 11) pp:6732

Publication Date(Web):October 5, 2015

DOI:10.1021/acscatal.5b01885

A silver-catalyzed intramolecular amination of alkynl-imine substrates has been extensively studied to build various isoquinoline derivatives efficiently. However, most of these transformations are limited to hydroamination, and the related oxidative reaction is quite rare. Importantly, the mechanistic details are still unknown, which retarded further progress in the field. In this work, a novel abnormal mesoionic carbene silver complex (MIC)nAg(I) was isolated and fully characterized as the key intermediate. Further investigation on the oxidative transformation of the silver complex reveals that successful oxidative halogenation could be achieved with NXS (X = Cl, Br, and I), as well as F+ reagent. Surprisingly, the fluorination reaction occurred in the presence of both strong (SelectFluor) and weak (NFSI) fluorinating reagents, although the F-Py-type reagent, whose oxidative potential lies between, is ineffective. Further mechanistic studies disclosed that (1) from kinetic data, the (MIC)Ag(I) complex was proved to be the reactive intermediate in the fluorination reaction, and pyridyl-oxazoline (Pyox) ligand could significantly improve this transformation; (2) from DFT calculation results, two different mechanistic pathways were suggested to be involved, a metathesis process in the case of NFSI promoted by the chelation of sulfonyl group toward the silver center and a redox process in the case of SelectFluor due to its strong oxidative potential.Keywords: abnormal mesoionic carbene; alkynl-imine; fluorination; oxidative; silver complex

Copper-Catalyzed Intermolecular Trifluoromethylazidation and Trifluoromethylthiocyanation of Allenes: Efficient Access to CF3-Containing Allyl Azides and Thiocyanates

Co-reporter:Na Zhu, Fei Wang, Pinhong Chen, Jinxing Ye, and Guosheng Liu

Organic Letters 2015 Volume 17(Issue 14) pp:3580-3583

Publication Date(Web):July 9, 2015

DOI:10.1021/acs.orglett.5b01677

A mild and efficient method for copper-catalyzed trifluoromethylazidation and trifluoromethylthiocyanation of allenes was explored. A series of CF3-containing allyl azides and thiocyanates were obtained with high yields and good stereoselectivities, which can be used for further transformation to some valuable compounds.

Copper-Catalyzed Intermolecular Trifluoromethylthiocyanation of Alkenes: Convenient Access to CF3-Containing Alkyl Thiocyanates

Co-reporter:Zhaoli Liang, Fei Wang, Pinhong Chen, and Guosheng Liu

Organic Letters 2015 Volume 17(Issue 10) pp:2438-2441

Publication Date(Web):April 24, 2015

DOI:10.1021/acs.orglett.5b00939

A highly selective and efficient approach for the direct trifluoromethylthiocyanation of alkenes has been developed using trimethylsilyl isothiocyanate (TMSNCS) as the thiocyanating agent and Togni reagent as the CF3 source in the presence of copper(I) catalyst. Both activated and unactivated alkenes work well to deliver various CF3-containing thiocyanates.

Palladium-Catalyzed Intramolecular Aminoacetoxylation of Unactivated Alkenes with Hydrogen Peroxide as Oxidant

Co-reporter:Haitao Zhu, Pinhong Chen, and Guosheng Liu

Organic Letters 2015 Volume 17(Issue 6) pp:1485-1488

Publication Date(Web):March 5, 2015

DOI:10.1021/acs.orglett.5b00373

A palladium-catalyzed intramolecular aminoacetoxylation of unactivated alkenes was developed in which H2O2 was used as the sole oxidant. A variety of 3-acetoxylated piperidines were obtained in good yields with good to excellent regio- and diastereoselectivities. Mechanistic study revealed that the addition of di(2-pyridyl) ketone (dpk) ligand was crucial to promote the oxidative cleavage of the C–Pd(II) bond by H2O2 to give the C–OAc bond.

Copper-Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3-Substituted Azirines and Aziridines

Co-reporter:Fei Wang;Na Zhu;Dr. Pinhong Chen;Dr. Jinxing Ye;Dr. Guosheng Liu

Angewandte Chemie 2015 Volume 127( Issue 32) pp:9488-9492

Publication Date(Web):

DOI:10.1002/ange.201503412

Abstract

A novel method for convenient access to CF₃-containing azirines has been developed, and involves a copper-catalyzed trifluoromethylazidation of alkynes and a photocatalyzed rearrangement. Both terminal and internal alkynes are compatible with the mild reaction conditions, thus delivering the CF₃-containing azirines in moderate to good yields. The azirines can be converted into various CF₃-substituted aziridines.

Copper-Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3-Substituted Azirines and Aziridines

Co-reporter:Fei Wang;Na Zhu;Dr. Pinhong Chen;Dr. Jinxing Ye;Dr. Guosheng Liu

Angewandte Chemie International Edition 2015 Volume 54( Issue 32) pp:9356-9360

Publication Date(Web):

DOI:10.1002/anie.201503412

Abstract

Advances and challenges in palladium-catalyzed intermolecular selective allylic C-H functionalization of alkenes

Co-reporter:Xiaoxu Qi;Pinhong Chen

Science China Chemistry 2015 Volume 58( Issue 8) pp:1249-1251

Publication Date(Web):2015 August

DOI:10.1007/s11426-015-5387-9

Copper-Catalyzed Intermolecular Trifluoromethylarylation of Alkenes: Mutual Activation of Arylboronic Acid and CF3+ Reagent

Co-reporter:Fei Wang, Dinghai Wang, Xin Mu, Pinhong Chen, and Guosheng Liu

Journal of the American Chemical Society 2014 Volume 136(Issue 29) pp:10202-10205

Publication Date(Web):July 1, 2014

DOI:10.1021/ja504458j

A novel copper-catalyzed intermolecular trifluoromethylarylation of alkenes is developed using less active ether-type Togni’s reagent under mild reaction conditions. Various alkenes and diverse arylboronic acids are compatible with these conditions. Preliminary mechanistic studies reveal that a mutual activation process between arylboronic acid and CF3+ reagent is essential. In addition, the reaction might involve a rate-determining transmetalation, and the final aryl C–C bond is derived from reductive elimination of the aryl(alkyl)Cu(III) intermediate.

Pd-Catalyzed Intramolecular Aminohydroxylation of Alkenes with Hydrogen Peroxide as Oxidant and Water as Nucleophile

Co-reporter:Haitao Zhu ; Pinhong Chen

Journal of the American Chemical Society 2014 Volume 136(Issue 5) pp:1766-1769

Publication Date(Web):January 13, 2014

DOI:10.1021/ja412023b

A palladium-catalyzed intramolecular aminohydroxylation of alkenes was developed, in which H2O2 was applied as the sole oxidant. A variety of related alkyl alcohols could be successfully obtained with good yields and excellent diastereoselectivities, which directly derived from oxidation cleavage of alkyl C-Pd bond by H2O2. Facile transformation of these products provided a powerful tool toward the synthesis of 2-amino-1,3-diols and 3-ol amino acids. Preliminary mechanistic studies revealed that major nucleophilic attack of water (SN2 type) at high-valent Pd center contributes to the final C-O(H) bond formation.

Copper-catalyzed fluorination of 2-pyridyl aryl bromides

Co-reporter:Xin Mu, Hao Zhang, Pinhong Chen and Guosheng Liu

Chemical Science 2014 vol. 5(Issue 1) pp:275-280

Publication Date(Web):27 Sep 2013

DOI:10.1039/C3SC51876K

Copper(I)-catalyzed cross-coupling of aryl halides is the subject of extensive interest in synthetic chemistry, but the related catalytic fluorination is unsuccessful. Herein, we have developed a novel copper-catalyzed fluorination of aryl bromides using AgF as the fluorine source. In this transformation a pyridyl directing group is essential for successful catalytic fluorination. A XANES/EXAFS study indicated that the presence of the pyridyl group is essential to stabilize the Cu(I) species and accelerate oxidative addition of the aryl bromide. Further mechanistic studies implicated a Cu(I/III) catalytic cycle in this Cu(I)-catalyzed fluorination, and final aryl C–F bond formation possibly proceeds through an irreversible reductive elimination of the ArCu(III)–F species. This rare report of catalytic fluorination by a copper catalyst provides a valuable foundation for further development of Cu(I)-catalyzed fluorination of aryl halides.

Branch-Selective Allylic C–H Carboxylation of Terminal Alkenes by Pd/sox Catalyst

Co-reporter:Hiroki Kondo, Feng Yu, Junichiro Yamaguchi, Guosheng Liu, and Kenichiro Itami

Organic Letters 2014 Volume 16(Issue 16) pp:4212-4215

Publication Date(Web):July 28, 2014

DOI:10.1021/ol5019135

A ligand-controlled branch-selective allylic C–H carboxylation through Pd catalysis is described. The developed catalytic system, which consists of Pd(OAc)2, sulfoxide–oxazoline (sox) as a ligand and benzoquinone as an oxidant, couples terminal alkenes and carboxylic acids to furnish the corresponding branched allylic esters with high regioselectivity.

Copper-Catalyzed Trifluoromethylthiolation of Aryl Halides with Diverse Directing Groups

Co-reporter:Jiabin Xu, Xin Mu, Pinhong Chen, Jinxing Ye, and Guosheng Liu

Organic Letters 2014 Volume 16(Issue 15) pp:3942-3945

Publication Date(Web):July 18, 2014

DOI:10.1021/ol501742a

The expansion of cross-coupling components in Cu-catalyzed C–X bond forming reactions have received much attention recently. A novel Cu-catalyzed trifluoromethylthiolation of aryl bromides and iodides with the assistance of versatile directing groups such as pyridyl, methyl ester, amide, imine and oxime was reported. CuBr was used as the catalyst, and 1,10-phenanthroline as the ligand. By changing the solvent from acetonitrile to DMF, the coupling process could even take place at room temperature.

AgF-Mediated Dialkylation of Activate Alkenes: An Efficient Access to Nitrile-Containing Spirooxindoles

Co-reporter:Liang Wu;Pinhong Chen

Chinese Journal of Chemistry 2014 Volume 32( Issue 8) pp:681-684

Publication Date(Web):

DOI:10.1002/cjoc.201400350

Abstract

A novel Ag-mediated dialkylation reaction of alkenes was disclosed, in which AgF was essential to activate CH bond of acetonitrile. This reaction provided an efficient way to nitrile-containing spirooxindoles from readily available (1H-indol-3-yl)methanamine derivatives.

Copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes: Convenient synthesis of CF3-containing alkyl nitriles

Co-reporter:Zhaoli Liang, Fei Wang, Pinhong Chen, Guosheng Liu

Journal of Fluorine Chemistry 2014 Volume 167() pp:55-60

Publication Date(Web):November 2014

DOI:10.1016/j.jfluchem.2014.04.004

•A novel copper-catalyzed cyanotrifluoromethylation of alkenes was reported.•Broad substrate scope included both styrene and unactivated alphatic alkenes.•The reaction condition is mild but the reaction is very fast.•A series of CF3-containing organonitriles was provided.A copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which the less reactive Togni reagent 2 was used as a CF3 source and TMSCN was employed as a cyano source. Both activated and unactivated alkenes were suitable for this transformation to give CF3-containing organonitriles under mild conditions.

Copper-Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF3-Containing Alkyl Azides

Co-reporter:Fei Wang;Xiaoxu Qi;Zhaoli Liang;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie 2014 Volume 126( Issue 7) pp:1912-1917

Publication Date(Web):

DOI:10.1002/ange.201309991

Abstract

A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF₃-containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF₃-containing amine derivatives.

Palladium-Catalyzed Cascade CH Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho-Trifluoroethylstyrenes

Co-reporter:Hao Zhang;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie 2014 Volume 126( Issue 38) pp:10338-10342

Publication Date(Web):

DOI:10.1002/ange.201403793

Abstract

A palladium-catalyzed selective CH bond trifluoroethylation of aryl iodides has been explored. The reaction allows for the efficient synthesis of a variety of ortho-trifluoroethyl-substituted styrenes. Preliminary mechanistic studies indicate that the reaction might involve a key Pd^IV intermediate, which is generated through the rate-determining oxidative addition of CF₃CH₂I to a palladacycle; the bulky nature of CF₃CH₂I influences the reactivity. Reductive elimination from the Pd^IV complex then leads to the formation of the aryl–CH₂CF₃ bond.

Palladium-Catalyzed Cascade CH Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho-Trifluoroethylstyrenes

Co-reporter:Hao Zhang;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie International Edition 2014 Volume 53( Issue 38) pp:10174-10178

Publication Date(Web):

DOI:10.1002/anie.201403793

Abstract

Copper-Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF3-Containing Alkyl Azides

Co-reporter:Fei Wang;Xiaoxu Qi;Zhaoli Liang;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie International Edition 2014 Volume 53( Issue 7) pp:1881-1886

Publication Date(Web):

DOI:10.1002/anie.201309991

Abstract

Palladium-catalyzed intermolecular fluoroesterification of styrenes: exploration and mechanistic insight

Co-reporter:Haihui Peng, Zheliang Yuan, Hao-yang Wang, Yin-long Guo and Guosheng Liu

Chemical Science 2013 vol. 4(Issue 8) pp:3172-3178

Publication Date(Web):21 May 2013

DOI:10.1039/C3SC50690H

A novel palladium-catalyzed intermolecular oxidative fluoroesterification of vinylarenes has been developed using NFSI, one of the mildest electrophilic fluorinating reagents. The reaction presents an efficient synthetic pathway to afford a series of α-monofluoromethylbenzyl carboxylates in good to excellent yields. Rather than following an electrophilic fluorination pathway, the reaction is initiated through oxidation of Pd(0) to a Pd(II) fluoride complex by NFSI, followed by fluoropalladation of a styrene to generate an α-monofluoromethylbenzyl–Pd intermediate. Generally, reductive elimination of benzyl–PdII complexes is favored with relatively strong oxy-nucleophiles to afford C–O bonds. This reaction, however, exhibited the opposite reactivity: strong acids with weak nucleophilicity, such as CF3CO2H and CCl3CO2H, were prone to afford the fluoroesterification product, while weak acids with strong nucleophilicity, such as HOAc and BzOH, did not deliver the C–O bond product. Further mechanistic studies determined that Csp3–Pd(O2CR), a key intermediate, was generated through ionic ligand exchange between benzyl–Pd(NZ2) and CF3CO2H, and the final C–O bond was possibly formed through reductive elimination of a high-valent Csp3–Pd(O2CR) complex via an SN2-type nucleophilic attack pathway.

Palladium-Catalyzed C–C Triple Bond Cleavage: Efficient Synthesis of 4H-Benzo[d][1,3]oxazin-4-ones

Co-reporter:Qilun Liu, Pinhong Chen, and Guosheng Liu

ACS Catalysis 2013 Volume 3(Issue 2) pp:178

Publication Date(Web):January 2, 2013

DOI:10.1021/cs300733s

Described herein is a new transformation of azidoalkynes by using a palladium catalyst, which involves a tandem process of aminopalladation of the alkyne and oxidative rearrangement. The reaction affords a variety of 4H-benzo[d][1,3]oxazin-4-ones. Mechanism studies support a Pd-catalyzed aminopalladation/oxidation/Baeyer–Villiger fragmentary sequence.Keywords: aminocyclization; azidoalkyne; C−C triple bond cleavage; oxidation; Pd catalyst

One-Pot Synthesis of 1-(Trifluoromethyl)-4-fluoro-1,2-dihydroisoquinolines and 4,4-Difluoro-1,2,3,4-tetrahydroisoquinolines

Co-reporter:Qilun Liu, Yichen Wu, Pinhong Chen, and Guosheng Liu

Organic Letters 2013 Volume 15(Issue 24) pp:6210-6213

Publication Date(Web):November 21, 2013

DOI:10.1021/ol403059z

A cascade approach to 1-(trifluoromethyl)-4-fluoro-1,2-dihydroisoquinolines and 4,4-difluorotetrahydroisoquinolines has been developed. The procedure involves a silver-catalyzed intramolecular aminofluorination of alkyne. This one-pot reaction provides an efficient way to synthesize various fluorinated isoquinolines.

Regioselective palladium-catalyzed intramolecular oxidative aminofluorination of unactivated alkenes

Co-reporter:Tao Wu, Jiashun Cheng, Pinhong Chen and Guosheng Liu

Chemical Communications 2013 vol. 49(Issue 77) pp:8707-8709

Publication Date(Web):31 Jul 2013

DOI:10.1039/C3CC44711A

A novel Pd-catalyzed regioselective intramolecular aminofluorination of unactivated alkenes has been developed, which is an efficient method for the synthesis of a variety of monofluoromethylated nitrogen-containing heterocycles.

Palladium-Catalyzed Intramolecular Fluorooxylation of Styrenes

Co-reporter:Zheliang Yuan;Haihui Peng

Chinese Journal of Chemistry 2013 Volume 31( Issue 7) pp:908-914

Publication Date(Web):

DOI:10.1002/cjoc.201300437

Abstract

A novel palladium-catalyzed intramolecular fluorooxylation of styrenes has been developed by using NFSI as fluorinating reagent. This reaction provides an efficient way for the synthesis of 2-aryl-3-fluorotetrahydrofuran derivatives.

Copper-Catalyzed Regioselective Fluorination of Allylic Halides

Co-reporter:Zuxiao Zhang;Fei Wang;Xin Mu;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie 2013 Volume 125( Issue 29) pp:7697-7701

Publication Date(Web):

DOI:10.1002/ange.201301891

Copper-Catalyzed Regioselective Fluorination of Allylic Halides

Co-reporter:Zuxiao Zhang;Fei Wang;Xin Mu;Dr. Pinhong Chen ;Dr. Guosheng Liu

Angewandte Chemie International Edition 2013 Volume 52( Issue 29) pp:7549-7553

Publication Date(Web):

DOI:10.1002/anie.201301891

Palladium-Catalyzed Intermolecular Aminoacetoxylation of Alkenes and the Influence of PhI(OAc)2 on Aminopalladation Stereoselectivity

Co-reporter:Claudio Martínez, Yichen Wu, Adam B. Weinstein, Shannon S. Stahl, Guosheng Liu, and Kilian Muñiz

The Journal of Organic Chemistry 2013 Volume 78(Issue 12) pp:6309-6315

Publication Date(Web):May 15, 2013

DOI:10.1021/jo400671q

A modified protocol has been identified for Pd-catalyzed intermolecular aminoacetoxylation of terminal and internal alkenes that enables the alkene to be used as the limiting reagent. The results prompt a reassessment of the stereochemical course of these reactions. X-ray crystallographic characterization of two of the products, together with isotopic labeling studies, show that the amidopalladation step switches from a cis-selective process under aerobic conditions to a trans-selective process in the presence of diacetoxyiodobenzene.

Ag(I)-Catalyzed Aminofluorination of Alkynes: Efficient Synthesis of 4-Fluoroisoquinolines and 4-Fluoropyrrolo[α]isoquinolines

Co-reporter:Tao Xu and Guosheng Liu

Organic Letters 2012 Volume 14(Issue 21) pp:5416-5419

Publication Date(Web):October 22, 2012

DOI:10.1021/ol3026507

A silver-catalyzed intramolecular oxidative aminofluorination of alkynes has been developed by using NFSI as a fluorinating reagent. This reaction represents an efficient method for the synthesis of various 4-fluoroisoquinolines and 4-fluoropyrrolo[α]isoquinolines.

Transition metal-catalyzed fluorination of multi carbon–carbon bonds: new strategies for fluorinated heterocycles

Co-reporter:Guosheng Liu

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 31) pp:6243-6248

Publication Date(Web):13 Jun 2012

DOI:10.1039/C2OB25702E

Transition metal catalysts have been developed for introducing fluorine into organic compounds. Recent progress in this area is reviewed with an emphasis on the selective fluorination of alkenes, alkynes and allenes. Regio- and stereoselective fluorination reactions are highlighted.

Organocatalyzed arylalkylation of activated alkenes via decarboxylation of PhI(O2CR)2: efficient synthesis of oxindoles

Co-reporter:Tao Wu, Hao Zhang, Guosheng Liu

Tetrahedron 2012 68(26) pp: 5229-5233

Publication Date(Web):

DOI:10.1016/j.tet.2012.03.051

Highly Selective Palladium-Catalyzed Intramolecular Chloroamination of Unactivated Alkenes by Using Hydrogen Peroxide as an Oxidant

Co-reporter:Guoyin Yin;Tao Wu ; Guosheng Liu

Chemistry - A European Journal 2012 Volume 18( Issue 2) pp:451-455

Publication Date(Web):

DOI:10.1002/chem.201102776

Palladium-Catalyzed Oxidative Aryltrifluoromethylation of Activated Alkenes at Room Temperature

Co-reporter:Xin Mu ; Tao Wu ; Hao-yang Wang ; Yin-long Guo

Journal of the American Chemical Society 2011 Volume 134(Issue 2) pp:878-881

Publication Date(Web):December 20, 2011

DOI:10.1021/ja210614y

A palladium-catalyzed intramolecular oxidative aryltrifluoromethylation reaction of activated alkenes has been explored. The reaction allows for an efficient synthesis of a variety of CF3-containing oxindoles. Preliminary mechanistic study indicated that the reaction involves a Csp3–PdIV(CF3) intermediate, which undergoes reductive elimination to afford a Csp3–CF3 bond.

Palladium-Catalyzed Tandem Fluorination and Cyclization of Enynes

Co-reporter:Haihui Peng and Guosheng Liu

Organic Letters 2011 Volume 13(Issue 4) pp:772-775

Publication Date(Web):January 20, 2011

DOI:10.1021/ol103039x

A novel palladium-catalyzed tandem fluorination and cyclization of enynes has been developed. A favorable cis-fluoropalladation is proposed as a key step to construct a vinyl−F bond, and the final Csp3−Pd bond is reduced by alcohol. This transformation represents an efficient road to synthesize fluorinated lactams.

Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes

Co-reporter:Tao Xu;Shuifa Qiu

Chinese Journal of Chemistry 2011 Volume 29( Issue 12) pp:2785-2790

Publication Date(Web):

DOI:10.1002/cjoc.201100340

Abstract

A novel palladium-catalyzed intramolecular oxidative aminofluorination of styrenes has been developed by using NFSI as fluorinating reagent. This reaction represented an efficient method for the synthesis of 2-aryl-3-fluoropyrrolidine derivatives.

Organocatalyzed cycloaddition of carbon dioxide to aziridines

Co-reporter:Yichen Wu, Guosheng Liu

Tetrahedron Letters 2011 Volume 52(Issue 48) pp:6450-6452

Publication Date(Web):30 November 2011

DOI:10.1016/j.tetlet.2011.09.092

An efficient and simple process for the fixation of carbon dioxide (CO2) to aziridine for the synthesis of 2-oxazolidinone by using DBN as catalyst, LiI as an additive under atmospheric pressure was developed. This chemical fixation of CO2 could also be carried out at room temperature with prolonged reaction time.An efficient and simple process for the fixation of carbon dioxide to aziridine by using DBN as catalyst, LiI as additive under atmospheric pressure was developed. This chemical fixation could also be carried out at room temperature with prolonged reaction time.

Palladium-catalyzed inter- and intramolecular hydroamination of styrenes coupled with alcohol oxidation using N-fluorobenzenesulfonimide as the oxidant

Co-reporter:Tao Xu, Shuifa Qiu, Guosheng Liu

Journal of Organometallic Chemistry 2011 696(1) pp: 46-49

Publication Date(Web):

DOI:10.1016/j.jorganchem.2010.07.015

Palladium-Catalyzed Oxidative Trifluoromethylation of Indoles at Room Temperature

Co-reporter:Xin Mu;Shujun Chen;Dr. Xingliang Zhen;Dr. Guosheng Liu

Chemistry - A European Journal 2011 Volume 17( Issue 22) pp:6039-6042

Publication Date(Web):

DOI:10.1002/chem.201100283

Palladium-Catalyzed Oxidative Arylalkylation of Activated Alkenes: Dual CH Bond Cleavage of an Arene and Acetonitrile

Co-reporter:Tao Wu;Xin Mu ;Dr. Guosheng Liu

Angewandte Chemie 2011 Volume 123( Issue 52) pp:12786-12789

Publication Date(Web):

DOI:10.1002/ange.201104575

Silver-Catalyzed Intramolecular Aminofluorination of Activated Allenes

Co-reporter:Tao Xu;Xin Mu;Haihui Peng ;Dr. Guosheng Liu

Angewandte Chemie 2011 Volume 123( Issue 35) pp:8326-8329

Publication Date(Web):

DOI:10.1002/ange.201103225

Palladium-Catalyzed Oxidative Arylalkylation of Activated Alkenes: Dual CH Bond Cleavage of an Arene and Acetonitrile

Co-reporter:Tao Wu;Xin Mu ;Dr. Guosheng Liu

Angewandte Chemie International Edition 2011 Volume 50( Issue 52) pp:12578-12581

Publication Date(Web):

DOI:10.1002/anie.201104575

Silver-Catalyzed Intramolecular Aminofluorination of Activated Allenes

Co-reporter:Tao Xu;Xin Mu;Haihui Peng ;Dr. Guosheng Liu

Angewandte Chemie International Edition 2011 Volume 50( Issue 35) pp:8176-8179

Publication Date(Web):

DOI:10.1002/anie.201103225

Palladium-Catalyzed Intermolecular Aminofluorination of Styrenes

Co-reporter:Shuifa Qiu ; Tao Xu ; Juan Zhou ; Yinlong Guo

Journal of the American Chemical Society 2010 Volume 132(Issue 9) pp:2856-2857

Publication Date(Web):February 11, 2010

DOI:10.1021/ja909716k

A novel palladium-catalyzed intermolecular aminofluorination of styrenes, with N-fluorobenzenesulfonimide (NFSI) functioning not only as a fluorinating reagent but also as an aminating reagent, has been developed. The reaction afforded vicinal fluoroamine products with very high regioselectivity. This transformation may involve fluoropalladation of styrene as a key step for C−F bond formation. The bidental nitrogen ligand is crucial to achieving the transformation successfully.

Palladium-Catalyzed Intramolecular Aminofluorination of Unactivated Alkenes

Co-reporter:Tao Wu ; Guoyin Yin

Journal of the American Chemical Society 2009 Volume 131(Issue 45) pp:16354-16355

Publication Date(Web):October 26, 2009

DOI:10.1021/ja9076588

A novel palladium-catalyzed intramolecular oxidative aminofluorination of unactivated alkenes has been developed, in which AgF was used as a key fluorinating reagent and PhI(OPiv)2 as oxidant. The reaction afforded vicinal fluoroamine products with very high regioselectivity. A Pd(II/IV) catalytic cycle was proposed, and preliminary mechanistic studies indicated that direct reductive elimination of Pd(IV) intermediates is favored, albeit competing with SN2 nucleophilic attack by fluorine, to form a C−F bond.

Brønsted Base-Modulated Regioselective Pd-Catalyzed Intramolecular Aerobic Oxidative Amination of Alkenes: Formation of Seven-Membered Amides and Evidence for Allylic C−H Activation

Co-reporter:Liang Wu, Shuifa Qiu and Guosheng Liu

Organic Letters 2009 Volume 11(Issue 12) pp:2707-2710

Publication Date(Web):May 20, 2009

DOI:10.1021/ol900941t

A novel palladium-catalyzed intramolecular aerobic oxidative allylic C−H amination of olefins has been developed. Brønsted base can modulate the regioselectivity, favoring the formation of 7-membered rings. Mechanistic studies using deuterium-labeled substrates as probes support a rate-determining allylic C−H activation/irreversible reductive elimination pathway.

Palladium-Catalyzed Intramolecular Hydroamination of Allenes Coupled to Aerobic Alcohol Oxidation

Co-reporter:Shuifa Qiu;Yunyang Wei Dr. Dr.

Chemistry - A European Journal 2009 Volume 15( Issue 12) pp:2751-2754

Publication Date(Web):

DOI:10.1002/chem.200802381

Palladium-Catalyzed Oxidative Cyclization of Enynes with Hydrogen Peroxide as the Oxidant

Co-reporter:Guoyin Yin Dr.

Angewandte Chemie International Edition 2008 Volume 47( Issue 29) pp:5442-5445

Publication Date(Web):

DOI:10.1002/anie.200801438

Palladium-Catalyzed Intermolecular Aerobic Oxidative Amination of Terminal Alkenes: Efficient Synthesis of Linear Allylamine Derivatives

Co-reporter:Guosheng Liu Dr.;Guoyin Yin ;Liang Wu

Angewandte Chemie International Edition 2008 Volume 47( Issue 25) pp:4733-4736

Publication Date(Web):

DOI:10.1002/anie.200801009

Palladium-Catalyzed Oxidative Cyclization of Enynes with Hydrogen Peroxide as the Oxidant

Co-reporter:Guoyin Yin Dr.

Angewandte Chemie 2008 Volume 120( Issue 29) pp:5522-5525

Publication Date(Web):

DOI:10.1002/ange.200801438

Palladium-Catalyzed Intermolecular Aerobic Oxidative Amination of Terminal Alkenes: Efficient Synthesis of Linear Allylamine Derivatives

Co-reporter:Guosheng Liu Dr.;Guoyin Yin ;Liang Wu

Angewandte Chemie 2008 Volume 120( Issue 25) pp:4811-4814

Publication Date(Web):

DOI:10.1002/ange.200801009

Palladium-catalyzed cascade cyclization for the construction of spiro-N,O-acetals

Co-reporter:Jiashun Cheng, Pinhong Chen and Guosheng Liu

Inorganic Chemistry Frontiers 2014 - vol. 1(Issue 3) pp:NaN293-293

Publication Date(Web):2014/03/06

DOI:10.1039/C4QO00002A

A facile Pd-catalyzed cascade cyclization of N-alkenylamine and pyruvic acids has been developed to construct spiro-N,O-acetals. This transformation was initiated by an intramolecular oxidative amination of alkenes, followed by hydrolysis to give a ketone intermediate, which further reacts with pyruvic acid to deliver the final spiro-N,O-acetals.

Copper-mediated/-catalyzed fluorination reactions: new routes to aryl fluorides

Co-reporter:Xin Mu and Guosheng Liu

Inorganic Chemistry Frontiers 2014 - vol. 1(Issue 4) pp:NaN433-433

Publication Date(Web):2014/03/06

DOI:10.1039/C4QO00003J

Recently, a series of transition metals have been extensively explored for the construction of aryl C–F bonds. The introduction of inexpensive copper reagents instead of Pd and Ag complexes would be promising methods for scalable production of aryl fluorides without concomitant hazardous wastes. This highlight mainly focused on recent advances in copper-mediated/-catalyzed fluorination reactions to construct aryl fluorides.

Regioselective palladium-catalyzed intramolecular oxidative aminofluorination of unactivated alkenes

Co-reporter:Tao Wu, Jiashun Cheng, Pinhong Chen and Guosheng Liu

Chemical Communications 2013 - vol. 49(Issue 77) pp:NaN8709-8709

Publication Date(Web):2013/07/31

DOI:10.1039/C3CC44711A

Copper-catalyzed fluorination of 2-pyridyl aryl bromides

Co-reporter:Xin Mu, Hao Zhang, Pinhong Chen and Guosheng Liu

Chemical Science (2010-Present) 2014 - vol. 5(Issue 1) pp:NaN280-280

Publication Date(Web):2013/09/27

DOI:10.1039/C3SC51876K

Palladium-catalyzed intermolecular fluoroesterification of styrenes: exploration and mechanistic insight

Co-reporter:Haihui Peng, Zheliang Yuan, Hao-yang Wang, Yin-long Guo and Guosheng Liu