The intermolecular asymmetric Heck reaction: Mechanistic and computational studies
UNSPECIFIED. (2001) The intermolecular asymmetric Heck reaction: Mechanistic and computational studies. HELVETICA CHIMICA ACTA, 84 (10). pp. 3043-3056. ISSN 0018-019XFull text not available from this repository.
Reactive intermediates in the asymmetric Heck reaction between aryl electrophiles and 2,3-dihydrofuran have been identified by NMR and mass spectrometry, with BINAP or the achiral diphosphanes dppp and dppf as ligands. The major cationic species observed is an alkylpalladium produced by addition of PdAr to the alkene followed by two further PdH-mediated isomerisation steps. This last species has been characterised at -60 degrees by H-1-, C-13-, and P-31-NMR, including HMQC techniques. The regiochemistry of PdAr and PdH addition to the reactant are opposite as defined by the reaction with (2-H-2(1))-2,3-dihydrofuran. DFT Calculations on the reaction pathway between [CH2(PH2)]PdPh+ and 2,3-dihydrofuran reveal several structurally interesting intermediates involving agostic beta -atom, ipso-Ph or reactant O-atom bonded to the Pd-atom, and elucidate the isomerisation pathway.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||HELVETICA CHIMICA ACTA|
|Publisher:||WILEY-V C H VERLAG GMBH|
|Number of Pages:||14|
|Page Range:||pp. 3043-3056|
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