Mechanistic Investigation of Iron-Catalyzed Coupling Reactions

Kleimark, Jonatan,1982Gothenburg University,Göteborgs universitet,Institutionen för kemi,Department of Chemistry (author)

The mechanism of the iron-catalyzed cross-coupling of aryl electrophiles with alkyl Grignard reagents is studied by a combination of GC monitoring, Hammett competition experiments, and DFT calculations. The reaction follows a pathway where an FeI complex, formed in situ, reacts in a rate-limiting oxidative addition with the aryl electrophile. A rapid thermoneutral transmetalation from a Grignard reagent occurs either before or after the oxidative addition, with little to differentiate between the two pathways. A reductive elimination of the resulting alkyl aryl FeIII complex closes the catalytic cycle. Iron in lower oxidation states can act as a competent precatalyst by oxidation into the FeI-FeIII cycle. FeII complexes can give FeI catalysts through reductive elimination of a bimetallic complex. Added ligands, dilution, and powerful aryl electrophiles all serve to increase the stability of the active catalyst, presumably by counteracting oligomerization of low-valent iron.

NATURVETENSKAP Kemi hsv//swe
NATURAL SCIENCES Chemical Sciences hsv//eng
cross-coupling • density functional calculations • homogeneous catalysis • iron • reaction mechanisms

Hedström, Anna,1983Gothenburg University,Göteborgs universitet,Institutionen för kemi,Department of Chemistry(Swepub:gu)xhannh (author)
Larsson, Per-Fredrik,1983Gothenburg University,Göteborgs universitet,Institutionen för kemi,Department of Chemistry(Swepub:gu)xlperm (author)
Johansson, Charlotte,1976Gothenburg University,Göteborgs universitet,Institutionen för kemi,Department of Chemistry(Swepub:gu)xjcham (author)
Norrby, Per-Ola,1962Gothenburg University,Göteborgs universitet,Institutionen för kemi,Department of Chemistry(Swepub:gu)xnorrp (author)
Göteborgs universitetInstitutionen för kemi (creator_code:org_t)

By the author/editor: Kleimark, Jonata ...; Hedström, Anna, ...; Larsson, Per-Fre ...; Johansson, Charl ...; Norrby, Per-Ola, ...

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