Intermolecular Oxidative Radical Addition to Aromatic Aldehydes: Direct Access to 1,4-and 1,5-Diketones via Silver-Catalyzed Ring-Opening Acylation of Cyclopropanols and Cyclobutanols

被引：69

作者：

Che, Chao ^{[1
]}

Qian, Zhaosheng ^{[1
]}

Wu, Mingchang ^{[1
]}

Zhao, Ying ^{[1
]}

Zhu, Gangguo ^{[1
]}

机构：

[1] Zhejiang Normal Univ, Dept Chem, Minist Educ Adv Catalysis Mat, Key Lab, 688 Yingbin Rd, Jinhua 321004, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 10期

基金：

中国国家自然科学基金;

关键词：

C BOND-CLEAVAGE; INTRAMOLECULAR ADDITION; 1,4-DICARBONYL COMPOUNDS; REGIOSPECIFIC SYNTHESIS; ELECTRON-TRANSFER; BETA-DIKETONES; FACILE ACCESS; KETONES; MECHANISM; CYCLOALKANOLS;

D O I：

10.1021/acs.joc.8b00666

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A novel silver-catalyzed ring-opening acylation of cyclopropanols and cyclobutanols is described. The reaction proceeds under mild and neutral conditions and provides a facile access to nonsymmetric 1,4- and 1,5-diketones in promising yields with broad substrate scope. Mechanistic studies including DFT calculations suggest the involvement of an uncommon water-assisted 1,2-HAT process, which is strongly exothermic and thus promotes addition of carbon radicals to aldehydes. In contrast to traditional reductive radical addition protocols, this work represents the first example of the intermolecular oxidative radical addition to aldehydes, thus offering a novel strategy for the direct synthesis of acyclic ketones from readily accessible aldehydes.

引用

页码：5665 / 5673

页数：9