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Article: Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: Substrate scope and mechanistic insights
Title | Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: Substrate scope and mechanistic insights |
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Authors | |
Keywords | alkynes density functional calculations diastereoselectivity gold tertiary amines |
Issue Date | 2011 |
Publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry |
Citation | Chemistry - A European Journal, 2011, v. 17 n. 46, p. 12932-12945 How to Cite? |
Abstract | An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu) 2(o-biphenyl)P}AuCl]/AgBF 4 (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu) 2(o-biphenyl)P}AuCl]/AgBF 4 (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Producing tertiary amines: The Au I-catalyzed tandem reaction of alkynes with secondary amines provides simple and efficient access to highly substituted tertiary amines with excellent yields and good to excellent diastereoselectivity. Mechanistic studies confirm that a possible reaction pathway involves intermolecular hydroamination via a monomeric cationic gold(I)-alkyne intermediate and subsequent transfer hydrogenation via a gold(I)-coordinated enamine intermediate. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Persistent Identifier | http://hdl.handle.net/10722/168581 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Liu, XY | en_US |
dc.contributor.author | Guo, Z | en_US |
dc.contributor.author | Dong, SS | en_US |
dc.contributor.author | Li, XH | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:21:02Z | - |
dc.date.available | 2012-10-08T03:21:02Z | - |
dc.date.issued | 2011 | en_US |
dc.identifier.citation | Chemistry - A European Journal, 2011, v. 17 n. 46, p. 12932-12945 | en_US |
dc.identifier.issn | 0947-6539 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168581 | - |
dc.description.abstract | An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu) 2(o-biphenyl)P}AuCl]/AgBF 4 (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu) 2(o-biphenyl)P}AuCl]/AgBF 4 (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Producing tertiary amines: The Au I-catalyzed tandem reaction of alkynes with secondary amines provides simple and efficient access to highly substituted tertiary amines with excellent yields and good to excellent diastereoselectivity. Mechanistic studies confirm that a possible reaction pathway involves intermolecular hydroamination via a monomeric cationic gold(I)-alkyne intermediate and subsequent transfer hydrogenation via a gold(I)-coordinated enamine intermediate. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | en_US |
dc.language | eng | en_US |
dc.publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry | en_US |
dc.relation.ispartof | Chemistry - A European Journal | en_US |
dc.subject | alkynes | - |
dc.subject | density functional calculations | - |
dc.subject | diastereoselectivity | - |
dc.subject | gold | - |
dc.subject | tertiary amines | - |
dc.subject.mesh | Alkynes - Chemistry | en_US |
dc.subject.mesh | Amines - Chemical Synthesis - Chemistry | en_US |
dc.subject.mesh | Catalysis | en_US |
dc.subject.mesh | Gold - Chemistry | en_US |
dc.subject.mesh | Hydrogenation | en_US |
dc.subject.mesh | Molecular Structure | en_US |
dc.subject.mesh | Stereoisomerism | en_US |
dc.title | Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: Substrate scope and mechanistic insights | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1002/chem.201101982 | en_US |
dc.identifier.pmid | 22012740 | - |
dc.identifier.scopus | eid_2-s2.0-80555135858 | en_US |
dc.identifier.hkuros | 205170 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-80555135858&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 17 | en_US |
dc.identifier.issue | 46 | en_US |
dc.identifier.spage | 12932 | en_US |
dc.identifier.epage | 12945 | en_US |
dc.identifier.isi | WOS:000297737900019 | - |
dc.publisher.place | Germany | en_US |
dc.identifier.scopusauthorid | Liu, XY=48662515100 | en_US |
dc.identifier.scopusauthorid | Guo, Z=36554069300 | en_US |
dc.identifier.scopusauthorid | Dong, SS=54401093400 | en_US |
dc.identifier.scopusauthorid | Li, XH=36012409200 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 0947-6539 | - |