Ligand-Less Iron-Catalyzed Aromatic Cross-Coupling Difluoromethylation of Grignard Reagents with Difluoroiodomethane

被引：11

作者：

Motohashi, Hirotaka ^{[1
]}

Kato, Miki ^{[1
]}

Mikami, Koichi ^{[1
]}

机构：

[1] Tokyo Inst Technol, Sch Mat & Chem Technol, Dept Chem Sci & Engn, Meguro Ku, Tokyo 1528552, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 10期

基金：

日本科学技术振兴机构;

关键词：

COPPER-MEDIATED DIFLUOROMETHYLATION; ARYL BORONIC ACIDS; ARYLBORONIC ACIDS; BASE-METAL; HALIDES; CHLORIDES; FLUORINE; ARENES; BROMIDES; ALKENYL;

D O I：

10.1021/acs.joc.9b00585

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Iron-catalyzed cross-coupling difluoromethylations of the Grignard reagents with difluoroiodomethane provide various aromatic difluoromethyl products in good yields, not employing sterically demanding ligands. Difluoromethylations proceed within 30 min at -20 degrees C with 2.0 equiv of the Grignard reagents and FeCl3 or Fe(acac)(3) (2.5 mol %). Mechanistic investigations clarify difluoromethyl radical intervention; Fe(0) ate is initially generated. Single-electron transfer from Fe(0) ate to difluoroiodomethane takes place. Recombination with aryl groups gives Ar-CF(2)Hs. The catalyst can be regenerated by the Grignard reagents.

引用

页码：6483 / 6490

页数：8

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