Evidence for spontaneous release of acrylates from a transition-metal complex upon coupling ethene or propene with a carboxylic moiety or CO(2).
The development of a new synthetic approach to acrylates based on the formation of alkyl esters of acrylic acids has been studied. A preformed Pd-COOMe moiety is used as a model system to investigate the insertion of an olefin into the Pd--C bond. The fast elimination of acrylate is observed. Density functional calculations support the experimental findings and allow the characterization of transition states along the reaction pathway. The first example of olefin/CO(2) coupling with facile release of ethyl acrylate is also presented.
Aresta
Michele
M
Department of Chemistry - CIRCC and University of Bari, Via Celso Ulpiani, 27, 70126 Bari, Italy.
Pastore
Carlo
C
Giannoccaro
Potenzo
P
Kovács
Gábor
G
Dibenedetto
Angela
A
Pápai
Imre
I
D000179:Acrylates / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry
D000179:Acrylates; D000475:Alkenes; D002264:Carboxylic Acids; D005030:Ethylenes; D009942:Organometallic Compounds; D028561:Transition Elements; D002245:Carbon Dioxide; C036216:ethylene; C013658:propylene