Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing an N-Heterocyclic Carbene Ligand

被引:79
|
作者
Hase, Shun [1 ]
Kayaki, Yoshihito [1 ]
Ikariya, Takao [1 ]
机构
[1] Tokyo Inst Technol, Grad Sch Sci & Engn, Dept Appl Chem, Meguro Ku, Tokyo 1528552, Japan
来源
ACS CATALYSIS | 2015年 / 5卷 / 09期
关键词
gold catalysis; carbon dioxide; carboxylative cyclization; alkenyl complex; cyclic urethane; INTRAMOLECULAR HYDROARYLATION; FUSED PYRIDOCOUMARINS; SELECTIVE SYNTHESIS; ATMOSPHERIC CO2; AMINO-ALCOHOLS; SYN-INSERTION; CYCLIC UREAS; ALKYNES; EFFICIENT; 2-OXAZOLIDINONES;
D O I
10.1021/acscatal.5b01335
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
The carboxylative cyclization of a range of propargylic amines using carbon dioxide (CO2) is promoted by IPr-gold(I) (IPr = 1,3-bis(2,6-diisopropyl-phenyl)-imidazol-2-ylidene) complexes to afford (Z)-5-alkylidene-2-oxazolidones in methanol under mild conditions, even in the absence of additives such as silver salts and bases. Investigation of the substrate scope shows that the catalytic performance is markedly retarded by the introduction of aromatic substituents at the alkyne terminus. The formation of alkenylgold(I) complexes as catalytic intermediate models is demonstrated by the treatment of methyl- and phenyl-substituted propargylamines with AuOH(IPr) under a CO2 atmosphere. A comparison of the reactivity of the alkenylgold(I) complexes clearly indicates that the alkenyl ligand attached to an alkyl group at the alpha position is more susceptible to protonolysis compared with that attached to a phenyl group. These results and kinetic experiments corroborate a catalytic cycle that involves the nucleophilic attack of carbamate at the C-C triple bond bound to the Au center and its subsequent protodeauration to release the cyclic urethane products.
引用
收藏
页码:5135 / 5140
页数:6
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