Intramolecular anti-Phosphinoauration of Alkynes: An FLP-Motivated Approach to Stable Aurated Phosphindolium Complexes

被引:37
作者
Arndt, Sebastian [1 ]
Hansmann, Max M. [1 ]
Motloch, Petr [1 ]
Rudolph, Matthias [1 ]
Rominger, Frank [1 ]
Hashmi, A. Stephen K. [1 ,2 ]
机构
[1] Heidelberg Univ, Organisch Chem Inst, D-69120 Heidelberg, Germany
[2] KAU, Fac Sci, Dept Chem, Jeddah 21589, Saudi Arabia
关键词
alkynes; frustrated lewis pair; gold; phosphines; C MULTIPLE BONDS; CATALYZED HYDROAMINATION; GOLD CATALYSIS; PHOSPHONIUM; CARBENES; LIGAND; HYDROPHOSPHINATION; CYCLIZATION; ACTIVATION; REACTIVITY;
D O I
10.1002/chem.201605914
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis of aurated phosphindolium complexes from easy accessible 1,5-alkynylphosphine derivatives has been studied by using gold(I) complexes featuring carbene and phosphine ligands as initiators. Upon formation of the mixed phosphine NHC/phosphine gold species, elevated temperatures induced the cyclization to give stable aurated phosphindolium salts, which is supported by DFT calculations. The key elementary step that comprises a yet unknown anti-phosphinoauration of an unactivated alkyne is favored if bulky NHC ligands are used which was analyzed by kinetic measurements. This concept could furthermore be extended to neutral (phosphindolium) AuCl complexes featuring the yet unknown phosphindole ligand.
引用
收藏
页码:2542 / 2547
页数:6
相关论文
共 62 条
[1]   EPR and DFT studies of the one-electron reduction product of phospholium cations [J].
Adkine, P ;
Cantat, T ;
Deschamps, E ;
Ricard, L ;
Mézailles, N ;
Le Floch, P ;
Geoffroy, M .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2006, 8 (07) :862-868
[2]  
Alcarazo M., 2010, ANGEW CHEM, V122, P2596
[3]   Steering the Surprisingly Modular π-Acceptor Properties of N-Heterocyclic Carbenes: Implications for Gold Catalysis [J].
Alcarazo, Manuel ;
Stork, Timon ;
Anoop, Anakuthil ;
Thiel, Walter ;
Fuerstner, Alois .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (14) :2542-2546
[4]  
[Anonymous], 2010, ANGEW CHEM INT EDIT, DOI [DOI 10.1002/ANGE.20, DOI 10.1002/ANGE.200905341]
[5]   Alternative synthetic methods through new developments in catalysis by gold [J].
Arcadi, Antonio .
CHEMICAL REVIEWS, 2008, 108 (08) :3266-3325
[6]   Gold-catalysed reactions of diynes [J].
Asiri, Abdullah M. ;
Hashmi, A. Stephen K. .
CHEMICAL SOCIETY REVIEWS, 2016, 45 (16) :4471-4503
[7]   Challenges in Catalytic Hydrophosphination [J].
Bange, Christine A. ;
Waterman, Rory .
CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (36) :12598-12605
[8]   IPr* an easily accessible highly hindered N-heterocyclic carbene [J].
Berthon-Gelloz, Guillaume ;
Siegler, Maxime A. ;
Spek, Anthony L. ;
Tinant, Bernard ;
Reek, Joost N. H. ;
Marko, Istvan E. .
DALTON TRANSACTIONS, 2010, 39 (06) :1444-1446
[9]   SYNTHESIS OF TRIPHENYLPHOSPHANE-EN-YNES AND PHOSPHINDOLES AS WELL AS X-RAY ANALYSES OF 2 PHOSPHINDOLES [J].
BUTTERS, T ;
WINTER, W .
CHEMISCHE BERICHTE-RECUEIL, 1984, 117 (03) :990-1002
[10]   Synthesis of transient and stable C-amino phosphorus ylides and their fragmentation into transient and stable carbenes [J].
Canac, Y ;
Conejero, S ;
Soleilhavoup, M ;
Donnadieu, B ;
Bertrand, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (02) :459-464