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Decarboxylative-Coupling of Allyl Acetate Catalyzed by Group 10 Organometallics, [(phen)M(CH3)]+.
- Source :
-
Journal of Organic Chemistry . 12/19/2014, Vol. 79 Issue 24, p12056-12069. 14p. - Publication Year :
- 2014
-
Abstract
- Gas-phase carbon-carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)]+ (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)]+ yields the organometallic complex, [(phen)M(CH3)]+, via decarboxylation. [(phen)M(CH3)]+ reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)]+, with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)]+, occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)]+, are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)]+. The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon-carbon bond coupling. DFT calculations suggest that carbon-carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00223263
- Volume :
- 79
- Issue :
- 24
- Database :
- Academic Search Index
- Journal :
- Journal of Organic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 100243455
- Full Text :
- https://doi.org/10.1021/jo501886w