Dual Hard/Soft Gold Catalysis: Intermolecular Friedel-Crafts-Type α-Amidoalkylation/Alkyne Hydroarylation Sequences by N-Acyliminium Ion Chemistry

被引:39
作者
Boiaryna, Liliana [1 ]
El Mkaddem, Mohamed Kamal [1 ]
Taillier, Catherine [1 ]
Dalla, Vincent [1 ]
Othman, Mohamed [1 ]
机构
[1] Univ Havre, CNRS, URCOM, EA 3221,FR 3038, F-76058 Le Havre, France
关键词
gold; homogeneous catalysis; hydroarylation; nitrogen heterocycles; reaction mechanisms; HIGHLY EFFICIENT; NUCLEOPHILIC-SUBSTITUTION; ADDITION-REACTIONS; BRONSTED ACID; ELECTROPHILIC ADDITION; PROPARGYLIC ALCOHOLS; ALKYLATION REACTIONS; ALLYLIC ALKYLATION; BOND FORMATION; MILD ACCESS;
D O I
10.1002/chem.201202225
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Gold catalysts have been applied in cascade-type reactions for the synthesis of different nitrogen-based compounds. The reactions likely proceed by a new gold-catalyzed cascade intermolecular alpha-amidoalkylation/intramolecular carbocyclization cascade process by unifying both the sigma- and pi-Lewis acid properties of the gold salts. In the first part of this report we show that the sigma-Lewis acidity of gold(I) and gold(III) could be exploited to efficiently catalyze the nucleophilic substitution of various alkoxy- and acetoxylactams. The reaction was found to be applicable to a wide range of cyclic N-acyliminium ion precursors and various nucleophiles, including allyltrimethylsilane, silyl enol ethers, arenes, and active methylene derivatives. As a logical progression of this study, a combined hard/soft binary catalytic gold system was then used to implement an unprecedented tandem intermolecular Friedel-Crafts amidoalkylation/intramolecular hydroarylation sequence allowing an expedient access to new, complex, fused polyheterocyclic structures from trivial materials.
引用
收藏
页码:14192 / 14200
页数:9
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