Palladium‐Catalyzed Negishi Cross‐Coupling Reaction of Difluoroiodomethane with Arylzinc Reagents

The catalytic difluoromethylation of arylzinc reagents with difluoroiodomethane in the presence of Pd2(dba)3/Xantphos is described to produce difluoromethyl products. Mechanistic investigations reveal that the oxidative addition of difluoroiodomethane to [(Xantphos)Pd0] provides trans‐[(Xantphos)PdI...

Full description

Saved in:
Bibliographic Details
Published in:Asian journal of organic chemistry 2019-05, Vol.8 (5), p.698-701
Main Authors: Nitta, Junki, Motohashi, Hirotaka, Aikawa, Kohsuke, Mikami, Koichi
Format: Article
Language:English
Subjects:
Arylzinc
Catalysis
Difluoroiodomethane
Difluoromethylation
Negishi Coupling
Organic chemistry
Palladium
Palladium Catalysis
Reagents
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The catalytic difluoromethylation of arylzinc reagents with difluoroiodomethane in the presence of Pd2(dba)3/Xantphos is described to produce difluoromethyl products. Mechanistic investigations reveal that the oxidative addition of difluoroiodomethane to [(Xantphos)Pd0] provides trans‐[(Xantphos)PdII(I)CF2H], which is subsequently transformed to cis‐[(Xantphos)PdII(Ph)CF2H] through transmetalation of phenylzinc. Next, reductive elimination occurs (t1/2=44.7 min at −10 °C) to give PhCF2H. The structural changes in [(Xantphos)PdII(Ph)CF2H] from trans to cis facilitates reductive elimination of PhCF2H. Catalytic difluoromethylation of arylzinc reagents with difluoroiodomethane in the presence of Pd2(dba)3/Xantphos is described to produce difluoromethyl products. Mechanistic investigations reveal that the oxidative addition of difluoroiodomethane to [(Xantphos)Pd0] provides trans‐[(Xantphos)PdII(I)CF2H], which is subsequently transformed to cis‐[(Xantphos)PdII(Ph)CF2H] through transmetalation of phenylzinc. Next, reductive elimination occurs to give PhCF2H.
ISSN:2193-5807
2193-5815
DOI:10.1002/ajoc.201900106