Precatalyst Effects on Pd-Catalyzed Cross-Coupling Difluoromethylation of Aryl Boronic Acids

被引：28

作者：

Hori, Kaishi ^{[1
]}

Motohashi, Hirotaka ^{[1
]}

Saito, Daichi ^{[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：

ACS CATALYSIS | 2019年 / 9卷 / 01期

关键词：

palladium; precatalyst; Suzuki-Miyaura cross-coupling; difluoromethylation; boronic acids; ARYLBORONIC ACIDS; PALLADIUM; FLUORINE; ACTIVATION; ARENES;

D O I：

10.1021/acscatal.8b03892

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 Pd-catalyzed difluoromethylation of aryl boronic acids with difluoroiodomethane is shown to provide the difluoromethyl compounds in high to moderate yields by Pd(PPh3)(2)/DPEphos catalyst in H2O/toluene. Mechanistic studies show that the oxidative addition by Pd(PPh3)(4) rather than Pd-2(dba)(3) precatalyst to difluoroiodomethane provides a square-planar trans-(PPh3)(2)Pd(II)(CF2H)I complex defined by X-ray crystallographic analysis. The trans-(PPh3)(2)Pd-(CF2H)I complex is transformed to cis-(PPh3)(2)Pd(CF2H)Ph detected by low temperature NMR analysis, via transmetalation with phenylboronic acids. The reductive elimination occurs via ligand exchange to DPEphosPd(CF2H)Ph to give Ph-CF2H (t(1/2) = 144.7 min at 20 degrees C) with formation of the Pd(0)(PPh3)(2)/DPEphos catalyst.

引用

页码：417 / 421

页数：9

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