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Tsuji-Trost Reaction of Non-Derivatized Allylic Alcohols
Stockholm Univ, Dept Organ Chem, S-10691 Stockholm, Sweden..
Stockholm Univ, Dept Organ Chem, S-10691 Stockholm, Sweden..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.ORCID iD: 0000-0001-5403-9902
Stockholm Univ, Dept Organ Chem, S-10691 Stockholm, Sweden..ORCID iD: 0000-0001-8735-5397
2018 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 14, p. 3488-3498Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcohols with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[kappa(2)-BiPhePhos][kappa(3)-C3H5] was observed. When ClPd[kappa(2)-BiPhePhos][eta(3)-C3H5] (complexI) was used as catalyst, non-reproducible results were obtained. Study of the complex by X-ray crystallography, (PNMR)-P-31 spectroscopy, and ESI-MS showed that a decomposition occurred where one of the phosphite ligands was oxidized to the corresponding phosphate, generating ClPd[kappa(1)-BiPhePhosphite-phosphate][eta(3)-C3H5] species (complexII). When the chloride was exchanged to the weaker coordinating OTf- counter ion the more stable Pd[kappa(2)-BiPhePhos][eta(3)-C3H5](+)+[OTf] (-) (complexIII) was formed. ComplexIII performed better and gave higher enantiospecificities in the substitution reactions. ComplexIII was evaluated in Tsuji-Trost reactions of stereogenic non-derivatized allylic alcohols. The desired products were obtained in good to excellent yields (71-98%) and enantiospecificities (73-99%) for both inter- and intramolecular substitution reactions with only water generated as a by-product. The methodology was applied to key steps in total synthesis of (S)-cuspareine and (+)-lentiginosine. A reaction mechanism involving a palladium hydride as a key intermediate in the activation of the hydroxyl group is proposed in the overall transformation.

Place, publisher, year, edition, pages
2018. Vol. 24, no 14, p. 3488-3498
Keywords [en]
asymmetric catalysis, cuspareine, OH activation, palladium, Tsuji-Trost reaction
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-350623DOI: 10.1002/chem.201705164ISI: 000426764400020PubMedID: 29178406OAI: oai:DiVA.org:uu-350623DiVA, id: diva2:1209304
Available from: 2018-05-22 Created: 2018-05-22 Last updated: 2018-05-22Bibliographically approved

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Orthaber, Andreas

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