A Redox-Switchable Gold(I) Complex for the Hydroamination of Acetylenes: A Convenient Way for Studying Ligand-Derived Electronic Effects

被引：19
作者：
Ruiz-Zambrana, Cesar [1 ]
Poyatos, Macarena [1 ]
Peris, Eduardo [1 ]
机构：
[1] Univ Jaume I RINGGOLD, Ctr Innovac Quim Avanzada ORFEO CINQA, Inst Adv Mat INAM, E-12071 Castellon de La Plana, Spain
来源：
ACS CATALYSIS | 2022年 / 12卷 / 08期
关键词：
redox-switchable; hydroamination of alkynes; gold; mechanism; N-heterocyclic carbene; homogeneous catalysis; ACTIVE MESOIONIC CARBENES; N-HETEROCYCLIC CARBENE; NON-INNOCENT LIGANDS; INTERMOLECULAR HYDROAMINATION; CATALYSIS; REACTIVITY; ALKYNES; DESIGN;
D O I：
10.1021/acscatal.2c00613
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NHC) ligand was preparedand characterized. The electrochemical studies reveal that thecomplex is able to undergo two successive reduction events,associated to the reduction of the NDI moiety of the NHC ligand.Once the redox-switchable properties of this Au(I) complex wereproven, the complex was tested in the hydroamination of terminalalkynes. The activity of the neutral complex was moderate-to-highfor this reaction, but the one-electron reduced species did notshow any activity in the reaction. The activity of the catalyst couldbe toggled offand on several times by successively adding areducing agent (cobaltocene) or an oxidant (acetylferroceniumtetrafluoroborate). The results indicate that the rate-determining step of the catalytic cycle is the nucleophilic attack of the amine on the Au-coordinated alkyne
引用
收藏
页码：4465 / 4472
页数：8
相关论文
共 54 条
[31]   Improving Homogeneous Cationic Gold Catalysis through a Mechanism-Based Approach [J].
Lu, Zhichao ;
Hammond, Gerald B. ;
Xu, Bo .
ACCOUNTS OF CHEMICAL RESEARCH, 2019, 52 (05) :1275-1288
[32]   Redox-active cyclopentadienyl Ni complexes with quinoid N-heterocyclic carbene ligands for the electrocatalytic hydrogen release from chemical fuels [J].
Luca, Oana R. ;
Huang, Daria L. ;
Takase, Michael K. ;
Crabtree, Robert H. .
NEW JOURNAL OF CHEMISTRY, 2013, 37 (11) :3402-3405
[33]   Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions [J].
Lyaskovskyy, Volodymyr ;
de Bruin, Bas .
ACS CATALYSIS, 2012, 2 (02) :270-279
[34]   Au(I)-catalyzed highly efficient intermolecular hydroamination of alkynes [J].
Mizushima, E ;
Hayashi, T ;
Tanaka, M .
ORGANIC LETTERS, 2003, 5 (18) :3349-3352
[35]   Hydroamination:: Direct addition of amines to alkenes and alkynes [J].
Mueller, Thomas E. ;
Hultzsch, Kai C. ;
Yus, Miguel ;
Foubelo, Francisco ;
Tada, Mizuki .
CHEMICAL REVIEWS, 2008, 108 (09) :3795-3892
[36]   Photoswitchable Metal-Mediated Catalysis: Remotely Tuned Alkene and Alkyne Hydroborations [J].
Neilson, Bethany M. ;
Bielawski, Christopher W. .
ORGANOMETALLICS, 2013, 32 (10) :3121-3128
[37]   Gold- and Platinum-Catalyzed Formal Markownikoff's Double Hydroamination of Alkynes: A Rapid Access to Tetrahydroquinazolinones and Angularly-Fused Analogues Thereof [J].
Patil, Nitin T. ;
Kavthe, Rahul D. ;
Raut, Vivek S. ;
Shinde, Valmik S. ;
Sridhar, Balasubramanian .
JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (04) :1277-1280
[38]   Carbophilic activation of π-systems via gold coordination: Towards regioselective access of intermolecular addition products [J].
Praveen, Chandrasekar .
COORDINATION CHEMISTRY REVIEWS, 2019, 392 :1-34
[39]   Redox-Switchable Cycloisomerization of Alkynoic Acids with Napthalenediimide-Derived N-Heterocyclic Carbene Complexes [J].
Ruiz-Zambrana, Cesar ;
Gutierrez-Blanco, Ana ;
Gonell, Sergio ;
Poyatos, Macarena ;
Peris, Eduardo .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2021, 60 (36) :20003-20011
[40]   Redox- and light-switchable N-heterocyclic carbenes: a "soup-to-nuts'' course on contemporary structure-activity relationships [J].
Ryu, Yeonkyeong ;
Ahumada, Guillermo ;
Bielawski, Christopher W. .
CHEMICAL COMMUNICATIONS, 2019, 55 (31) :4451-4466
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