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. 2015 Jan 2;54(1):201-6.
doi: 10.1002/anie.201408814. Epub 2014 Nov 5.

Early main group metal catalysis: how important is the metal?

Affiliations

Early main group metal catalysis: how important is the metal?

Johanne Penafiel et al. Angew Chem Int Ed Engl. .

Abstract

Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal-alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca(2+) . The role of the metal was evaluated by a study using the metal-free catalysts: [Ph2 N(-) ][Me4 N(+) ] and [Ph3 C(-) ][Me4 N(+) ]. These "naked" amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of ArNCO and RNCNR (R=alkyl) by Ph2 NH. For the intramolecular hydroamination of unactivated CC bonds in H2 CCHCH2 CPh2 CH2 NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.

Keywords: Schwesinger base; homogeneous catalysis; hydroamination; main group metals.

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