Qiu Wang

Find an error

Name: Wang, Qiu

Organization: Duke University , USA

Department: Department of Chemistry

Title: Assistant(PhD)

TOPICS

Organic Chemistry

Amination

Chemicals
References

Site-Selective Copper-Catalyzed Amination and Azidation of Arenes and Heteroarenes via Deprotonative Zincation

Co-reporter:Charles E. Hendrick, Katie J. Bitting, Seoyoung Cho, and Qiu Wang

Journal of the American Chemical Society August 23, 2017 Volume 139(Issue 33) pp:11622-11622

Publication Date(Web):July 28, 2017

DOI:10.1021/jacs.7b07661

Arene amination is achieved by site-selective C–H zincation followed by copper-catalyzed coupling with O-benzoylhydroxylamines under mild conditions. Key to this success is ortho-zincation mediated by lithium amidodiethylzincate base that is effective for a wide range of arenes, including nonactivated arenes bearing simple functionalities such as fluoride, chloride, ester, amide, ether, nitrile, and trifluoromethyl groups as well as heteroarenes including indole, thiophene, pyridine, and isoquinoline. An analogous C–H azidation is also accomplished using azidoiodinane for direct introduction of a useful azide group onto a broad scope of arenes and heteroarenes. These new transformations offer rapid access to valuable and diverse chemical space of aminoarenes. Their broad applications in organic synthesis and drug discovery are demonstrated in the synthesis of novel analogues of natural product (−)-nicotine and antidepressant sertraline by late-stage amination and azidation reactions.

Emerging Developments Using Nitrogen–Heteroatom Bonds as Amination Reagents in the Synthesis of Aminoarenes

Co-reporter:Charles E. Hendrick and Qiu Wang

The Journal of Organic Chemistry 2017 Volume 82(Issue 2) pp:

Publication Date(Web):January 6, 2017

DOI:10.1021/acs.joc.6b02792

Aminoarenes constitute valuable building blocks in organic synthesis and an essential skeleton ubiquitously found in ligands, agrochemicals, and pharmaceuticals. This Synopsis presents recent amination methods using nitrogen–heteroatom bonds as a powerful and versatile platform to rapidly synthesize diverse aminoarenes, with a focus on aryne amino functionalization and transition-metal-catalyzed arene C–H amination.

Copper-catalyzed aminoalkynylation of alkenes with hypervalent iodine reagents

Co-reporter:Kun Shen

Chemical Science (2010-Present) 2017 vol. 8(Issue 12) pp:8265-8270

Publication Date(Web):2017/11/20

DOI:10.1039/C7SC03420B

A copper-catalyzed aminoalkynylation of alkenes is achieved with ethynylbenziodoxolone (EBX) reagents under mild conditions with only 1 mol% copper catalyst. This transformation allows for rapid construction of diverse important azahetereocycles and installation of valuable alkyne groups in one step. The developed method features remarkable substrate scope for both terminal and internal alkenes as well as different alkynyl groups, presenting great potential for broad applications in synthesis, bioconjugation, and molecular imaging.

Titelbild: Diazirines as Potential Molecular Imaging Tags: Probing the Requirements for Efficient and Long-Lived SABRE-Induced Hyperpolarization (Angew. Chem. 40/2017)

Co-reporter:Dr. Kun Shen;Dr. Angus W. J. Logan;Dr. Johannes F. P. Colell;Junu Bae;Gerardo X. Ortiz Jr.; Thomas Theis; Warren S. Warren; Steven J. Malcolmson; Qiu Wang

Angewandte Chemie 2017 Volume 129(Issue 40) pp:12179-12179

Publication Date(Web):2017/09/25

DOI:10.1002/ange.201707296

Diazirine sind dank ihrer Biokompatibilität und ihres leichten Einbaus in verschiedenartige Verbindungen aussichtsreiche molekulare Marker für Kernspintomographie und NMR-Spektroskopie. In ihrer Zuschrift auf S. 12280 zeigen W. S. Warren, S. J. Malcolmson, Q. Wang und Mitarbeiter anhand eines entsprechenden Cholinderivats, dass 15N2-Diazirin-Motive eine lang anhaltende Polarisation durch die einfache SABRE-SHEATH-Hyperpolarisationsmethode unterstützen.

Cover Picture: Diazirines as Potential Molecular Imaging Tags: Probing the Requirements for Efficient and Long-Lived SABRE-Induced Hyperpolarization (Angew. Chem. Int. Ed. 40/2017)

Co-reporter:Dr. Kun Shen;Dr. Angus W. J. Logan;Dr. Johannes F. P. Colell;Junu Bae;Gerardo X. Ortiz Jr.; Thomas Theis; Warren S. Warren; Steven J. Malcolmson; Qiu Wang

Angewandte Chemie International Edition 2017 Volume 56(Issue 40) pp:12015-12015

Publication Date(Web):2017/09/25

DOI:10.1002/anie.201707296

Diazirines are an attractive class of potential molecular tags for magnetic resonance imaging owing to their biocompatibility and ease of incorporation into a large variety of molecules. In their Communication on page 12112 ff., W. S. Warren, S. J. Malcolmson, Q. Wang, and co-workers show with a 15N2-diazirine-containing choline derivative that 15N2-diazirine motifs are capable of supporting long-lasting polarization by the simple SABRE-SHEATH hyperpolarization method, making then promising as tags for NMR/MRI imaging.

Diazirines as Potential Molecular Imaging Tags: Probing the Requirements for Efficient and Long-Lived SABRE-Induced Hyperpolarization

Co-reporter:Dr. Kun Shen;Dr. Angus W. J. Logan;Dr. Johannes F. P. Colell;Junu Bae;Gerardo X. Ortiz Jr.; Thomas Theis; Warren S. Warren; Steven J. Malcolmson; Qiu Wang

Angewandte Chemie International Edition 2017 Volume 56(Issue 40) pp:12112-12116

Publication Date(Web):2017/09/25

DOI:10.1002/anie.201704970

AbstractDiazirines are an attractive class of potential molecular tags for magnetic resonance imaging owing to their biocompatibility and ease of incorporation into a large variety of molecules. As recently reported, 15N2-diazirine can be hyperpolarized by the SABRE-SHEATH method, sustaining both singlet and magnetization states, thus offering a path to long-lived polarization storage. Herein, we show the generality of this approach by illustrating that the diazirine tag alone is sufficient for achieving excellent signal enhancements with long-lasting polarization. Our investigations reveal the critical role of Lewis basic additives, including water, on achieving SABRE-promoted hyperpolarization. The application of this strategy to a 15N2-diazirine-containing choline derivative demonstrates the potential of 15N2-diazirines as molecular imaging tags for biomedical applications.

Diazirines as Potential Molecular Imaging Tags: Probing the Requirements for Efficient and Long-Lived SABRE-Induced Hyperpolarization

Co-reporter:Dr. Kun Shen;Dr. Angus W. J. Logan;Dr. Johannes F. P. Colell;Junu Bae;Gerardo X. Ortiz Jr.; Thomas Theis; Warren S. Warren; Steven J. Malcolmson; Qiu Wang

Angewandte Chemie 2017 Volume 129(Issue 40) pp:12280-12284

Publication Date(Web):2017/09/25

DOI:10.1002/ange.201704970

Copper-Catalyzed Amino Lactonization and Amino Oxygenation of Alkenes Using O-Benzoylhydroxylamines

Co-reporter:Brett N. Hemric; Kun Shen

Journal of the American Chemical Society 2016 Volume 138(Issue 18) pp:5813-5816

Publication Date(Web):April 25, 2016

DOI:10.1021/jacs.6b02840

A copper-catalyzed amino lactonization of unsaturated carboxylic acids has been achieved as well as the analogous intermolecular three-component amino oxygenation of olefins. The transformation features mild conditions and a remarkably broad substrate scope, offering a novel and efficient approach to construct a wide range of amino lactones as well as 1,2-amino alcohol derivatives. Mechanistic studies suggest that the reaction proceeds via a distinctive O-benzoylhydroxylamine-promoted electrophilic amination of alkenes.

Arylation, Vinylation, and Alkynylation of Electron-Deficient (Hetero)arenes Using Iodonium Salts

Co-reporter:Chuan Liu and Qiu Wang

Organic Letters 2016 Volume 18(Issue 19) pp:5118-5121

Publication Date(Web):September 8, 2016

DOI:10.1021/acs.orglett.6b02550

Arylation, vinylation, and alkynylation of electron-deficient arenes and heteroarenes have been achieved by chemoselective C–H zincation followed by copper-catalyzed coupling reactions using iodonium salts. This approach offers a direct and general access to a wide scope of (hetero)biaryls as well as alkenylated and alkynylated heteroarenes under mild conditions. It is particularly useful and valuable for the rapid and modular synthesis of diverse (hetero)aryl compounds, as demonstrated in the synthesis of transient receptor potential vanilloid 1 (TRPV1) antagonists and angiotensin II receptor type 1 (AT1 receptor) antagonists.

Direct and cost-efficient hyperpolarization of long-lived nuclear spin states on universal 15N2-diazirine molecular tags

Co-reporter:Thomas Theis;Gerardo X. Ortiz Jr.;Kevin E. Claytor;Yesu Feng;Angus W. J. Logan;William P. Huhn;Volker Blum;Eduard Y. Chekmenev;Steven J. Malcolmson;Warren S. Warren

Science Advances 2016 Volume 2(Issue 3) pp:e1501438

Publication Date(Web):25 Mar 2016

DOI:10.1126/sciadv.1501438

More than 10,000-fold enhanced magnetic resonance signals with >20-min signal lifetimes on universal biomolecular markers.

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines

Co-reporter:Kun Shen and Qiu Wang

Chemical Science 2015 vol. 6(Issue 7) pp:4279-4283

Publication Date(Web):18 May 2015

DOI:10.1039/C5SC00897B

A copper-catalyzed regio- and stereoselective diamination of unactivated alkenes has been developed with O-acylhydroxylamines as electrophilic nitrogen sources and oxidants. This method provides the first example of metal-catalyzed alkene diamination for directly installing an electron-rich amino group and extends the diamination scope for the synthesis of diverse 1,2-diamines. It offers a rapid and efficient approach to construct a wide range of 1,2-diamines that are an important structural motif in organic synthesis, medicines, catalysts and ligands.

Synthesis of o-Aminophenols via a Formal Insertion Reaction of Arynes into Hydroxyindolinones

Co-reporter:Zhilong Chen and Qiu Wang

Organic Letters 2015 Volume 17(Issue 24) pp:6130-6133

Publication Date(Web):December 8, 2015

DOI:10.1021/acs.orglett.5b03147

A novel approach toward the synthesis of sterically hindered o-aminophenols has been achieved by a formal aryne insertion into hydroxyindolinones. This transformation offers a rapid and efficient entry to diverse o-aminophenol scaffolds under mild transition-metal-free conditions. The reaction involves the addition of hydroxyindolinones to arynes followed by a chemo- and regioselective [1,3]-rearrangement. Furthermore, the reactions of N-hydroxyindoles and arynes were found to provide the C3-aryl indole products via an alternative [3,3]-rearrangement pathway.

Synthesis of ortho-Haloaminoarenes by Aryne Insertion of Nitrogen–Halide Bonds

Co-reporter:Charles E. Hendrick and Qiu Wang

The Journal of Organic Chemistry 2015 Volume 80(Issue 2) pp:1059-1069

Publication Date(Web):December 11, 2014

DOI:10.1021/jo502541t

A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of N–X insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.

Selective α-amination and α-acylation of esters and amides via dual reactivity of O-acylhydroxylamines toward zinc enolates

Co-reporter:Stacey L. McDonald and Qiu Wang

Chemical Communications 2014 vol. 50(Issue 19) pp:2535-2538

Publication Date(Web):09 Jan 2014

DOI:10.1039/C3CC49296F

Selective α-amination and α-acylation of esters and amides have been developed, employing O-acylhydroxylamines as a dually reactive aminating and acylating reagent. Treatment of zinc enolates with O-acylhydroxylamines provides solely 1,3-dicarbonyl compounds under mild conditions. Introduction of a copper catalyst into the system shifts the reactivity entirely, yielding α-amination products exclusively.

One-Pot Synthesis of 3-Azido- and 3-Aminopiperidines by Intramolecular Cyclization of Unsaturated Amines

Co-reporter:Gerardo X. Ortiz Jr., Bora Kang, and Qiu Wang

The Journal of Organic Chemistry 2014 Volume 79(Issue 2) pp:571-581

Publication Date(Web):December 20, 2013

DOI:10.1021/jo4022666

A highly efficient one-pot synthesis of 3-azidopiperidines has been achieved by an intramolecular cyclization of unsaturated amines that allows for the nucleophilic installation of an azide moiety. This method unlocks the versatile employment of the azide functionality in the preparation and biological studies of piperidine-containing structures. This strategy has been expanded for the direct incorporation of a variety of nitrogen nucleophiles, and thus it provides a rapid and modular synthesis of 3-amino and 3-amidopiperidines of important pharmaceutical and biological relevance. Particularly noteworthy is that the regioselectivity of this transformation enables the formation of the anti-Markovnikov-type adduct, complementing Markovnikov-based olefin amino functionalization methods.

Copper-Catalyzed Electrophilic Amination of Heteroarenes and Arenes by CH Zincation

Co-reporter:Stacey L. McDonald;Charles E. Hendrick ;Dr. Qiu Wang

Angewandte Chemie 2014 Volume 126( Issue 18) pp:4755-4758

Publication Date(Web):

DOI:10.1002/ange.201311029

Abstract

Direct amination of heteroarenes and arenes has been achieved in a one-pot CH zincation/copper-catalyzed electrophilic amination procedure. This amination method provides an efficient and rapid approach to access a diverse range of heteroaromatic and aromatic amines including those previously inaccessible using CH amination methods. The mild reaction conditions and good functional-group compatibility demonstrate its great potential for the synthesis of important and complex amines.

Copper-Catalyzed -Amination of Phosphonates and Phosphine Oxides: A Direct Approach to -Amino Phosphonic Acids and Derivatives

Co-reporter:Stacey L. McDonald ;Dr. Qiu Wang

Angewandte Chemie 2014 Volume 126( Issue 7) pp:1898-1902

Publication Date(Web):

DOI:10.1002/ange.201308890

Abstract

A direct approach to important α-amino phosphonic acids and its derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of CN bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope.

Copper-Catalyzed Electrophilic Amination of Heteroarenes and Arenes by CH Zincation

Co-reporter:Stacey L. McDonald;Charles E. Hendrick ;Dr. Qiu Wang

Angewandte Chemie International Edition 2014 Volume 53( Issue 18) pp:4667-4670

Publication Date(Web):

DOI:10.1002/anie.201311029

Abstract

Copper-Catalyzed -Amination of Phosphonates and Phosphine Oxides: A Direct Approach to -Amino Phosphonic Acids and Derivatives

Co-reporter:Stacey L. McDonald ;Dr. Qiu Wang

Angewandte Chemie International Edition 2014 Volume 53( Issue 7) pp:1867-1871

Publication Date(Web):

DOI:10.1002/anie.201308890

Abstract

An Efficient Synthesis of Fluorinated Azaheterocycles by Aminocyclization of Alkenes

Co-reporter:Hai-Tsang Huang, Tyler C. Lacy, Barbara Błachut, Gerardo X. Ortiz Jr., and Qiu Wang

Organic Letters 2013 Volume 15(Issue 8) pp:1818-1821

Publication Date(Web):April 1, 2013

DOI:10.1021/ol4003866

A general and efficient approach to important fluorinated azaheterocycles has been developed by incorporating nucleophilic fluorination into alkene difunctionalization. This intramolecular aminofluorination transformation of alkenes has been achieved via the aminocyclization of reactive unsaturated N-iodoamines, which can be generated in situ from either unsaturated N-chloramines or their amine precursors in a one-pot protocol.

Insertion of Arynes into N-Halo Bonds: A Direct Approach to o-Haloaminoarenes

Co-reporter:Charles E. Hendrick, Stacey L. McDonald, and Qiu Wang

Organic Letters 2013 Volume 15(Issue 13) pp:3444-3447

Publication Date(Web):June 24, 2013

DOI:10.1021/ol401518c

A new approach to access o-haloaminoarenes has been achieved by insertion of arynes into a nitrogen–halide bond (N–X). This transition-metal-free transformation displays a broad substrate scope of arynes, good compatibility with functional groups, and high regioselectivity. Representative transformations of the o-haloaminoarenes are described to highlight their utility for rapid access to diversely functionalized aminoarene derivatives.

Copper-catalyzed aminotrifluoromethylation of alkenes: a facile synthesis of CF3-containing lactams

Co-reporter:Kun Shen and Qiu Wang

Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 2) pp:NaN226-226

Publication Date(Web):2015/12/10

DOI:10.1039/C5QO00353A

Copper-catalyzed aminotrifluoromethylation of alkenes using amides as nucleophiles has been developed. It provides a rapid and efficient access to a variety of CF3-containing lactams. The reaction proceeds under mild conditions with a good scope and functional group tolerance, offering a valuable method to prepare CF3-containing lactams that are of great potential in pharmaceuticals and agrochemicals.

Selective α-amination and α-acylation of esters and amides via dual reactivity of O-acylhydroxylamines toward zinc enolates

Co-reporter:Stacey L. McDonald and Qiu Wang

Chemical Communications 2014 - vol. 50(Issue 19) pp:NaN2538-2538

Publication Date(Web):2014/01/09

DOI:10.1039/C3CC49296F

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines

Co-reporter:Kun Shen and Qiu Wang

Chemical Science (2010-Present) 2015 - vol. 6(Issue 7) pp:NaN4283-4283

Publication Date(Web):2015/05/18

DOI:10.1039/C5SC00897B