Sterically goverend selectivity in palladium-assisted allylic alkylation
2011 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 30, 230-238 p.Article in journal (Refereed) Published
The selectivity in the Pd-assisted allylic alkylation has been investigated in a system with a ligand tethered to the allylic moiety. Isolation of (η3-allyl)Pd complexes and stoichiometric reaction with malonate nucleophiles allowed separation of various factors influencing the regioselectivity in a system that cannot undergo apparent rotation. Unexpectedly, trans effects were found to have only a minor influence on the selectivity, whereas changing the tether length could shift the preference from favored internal to dominant terminal attack. DFT-assisted analysis revealed that the dominant selectivity-determiningfactors are the forced rotation of the allylic moiety and an important steric repulsion from a syn-alkyl substituent
Place, publisher, year, edition, pages
2011. Vol. 30, 230-238 p.
IdentifiersURN: urn:nbn:se:su:diva-70977DOI: 10.1021/om1007264OAI: oai:DiVA.org:su-70977DiVA: diva2:483434
FunderSwedish Research Council