Conformational preferences and enantiodiscrimination of phosphino-4-(1-hydroxyalkyl)oxazoline-metal-olefin complexes resulting from an OH-metal hydrogen bond
2005 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 70, no 24, 9882-9891 p.Article in journal (Refereed) Published
Phosphinooxazolines carrying (1-hydroxy-1-phenyl)methyl and (1-methoxy-1-phenyl)methyl substituents in the 4 position of the oxazoline ring exhibit contrasting behavior in Pd-and Ir-catalyzed allylic alkylations. Whereas catalysts with the methoxy-containing ligand generally provide products with high ee's, use of catalysts prepared from the hydroxy-containing ligand results in products with low ee's or even racemates. DFT calculations suggest the presence of a hydrogen bond with Pd(0) as the proton acceptor in the hydroxy-containing olefin-Pd(0) complexes, which induces a conformational change in the ligand, leading to different stereoselectivity.
Place, publisher, year, edition, pages
2005. Vol. 70, no 24, 9882-9891 p.
Catalyst selectivity; Catalysts; Conformations; Hydrogen bonds; Molecular structure; Olefins; Stereochemistry; Substitution reactions
IdentifiersURN: urn:nbn:se:kth:diva-7125DOI: 10.1021/jo051610qISI: 000233539200027ScopusID: 2-s2.0-28044432560OAI: oai:DiVA.org:kth-7125DiVA: diva2:12042
QC 201007092007-05-162007-05-162010-07-09Bibliographically approved