One-Pot Synthesis of Benzene-Fused Medium-Ring Ketones: Gold Catalysis-Enabled Enolate Umpolung Reactivity

被引：99

作者：

Xu, Zhou ^{[1
,2
]}

Chen, Hongyi ^{[1
]}

Wang, Zhixun ^{[1
]}

Ying, Anguo ^{[1
,3
]}

Zhang, Liming ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[2] Xuzhou Med Coll, Dept Chem, Xuzhou 221004, Peoples R China

[3] Taizhou Univ, Taizhou 317000, Zhejiang, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 17期

基金：

美国国家科学基金会;

关键词：

PYRIDINE-N-OXIDE; OXIDATIVE CYCLIZATION; P; N-BIDENTATE LIGAND; ALKYNE OXIDATION; ARYL ETHERS; CARBENES; FUNCTIONALIZATION; STRATEGY;

D O I：

10.1021/jacs.6b02533

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Enolate umpolung reactivities offer valuable and potentially unique alternatives over the enolate counterparts for the construction of ubiquitous carbonyl compounds. We disclose here that N-alkenoxypyridinium salts, generated readily upon gold-catalyzed additions of protonated pyridine N-oxide to C-C triple bonds of unactivated terminal alkynes, display versatile enolate umpolung chemistry upon heating and react with tethered arene nucleophiles in an S(N)2' manner. In a synthetically efficient one-pot, two-step process, this chemistry enables expedient preparation of valuable benzo-fused seven-/eight-membered cyclic ketones, including those of O-/N-heterocycles, from easily accessible aryl-substituted linear alkyne substrates. The reaction yields can be up to 87%.

引用

页码：5515 / 5518

页数：4

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