OH–Pd(0) Interaction as a Stabilizing Factor in Palladium-Catalyzed Allylic Alkylations
2004 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 101, no 15, 5400-5404 p.Article in journal (Refereed) Published
In palladium-catalyzed alkylations of allylic acetates with malonate as nucleophile, catalysts with oxazoline ligands bearing hydroxymethyl substituents in 4-position have been shown by density functional theory computations to undergo a conformational change on nucleophilic attack, which is accompanied by reduction of Pd(II) to Pd(0). The conformations of the Pd(0) complexes were shown to be governed by the presence of a hydrogen bond with the metal center acting as a hydrogen bond acceptor. The conformational change, which is absent in catalysts with O-alkylated analogs, largely affects the enantioselectivity of the catalytic process. This process is a previously uninvestigated example of where this type of weak hydrogen bond has been shown to influence the stereochemistry of a chemical reaction.
Place, publisher, year, edition, pages
2004. Vol. 101, no 15, 5400-5404 p.
cetic acid; allyl acetate; allyl compound; hydroxide; ligand; malonic acid; oxazoline derivative; palladium; unclassified drug; alkylation; article; catalyst; chemical reaction; conformation; conformational transition; density functional theory; enantioselectivity; hydrogen bond; priority journal; stereochemistry
IdentifiersURN: urn:nbn:se:kth:diva-7123DOI: 10.1073/pnas.0307084101ISI: 000220861500019ScopusID: 2-s2.0-1842862757OAI: oai:DiVA.org:kth-7123DiVA: diva2:12040
QC 201007092007-05-162007-05-162012-03-21Bibliographically approved