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Tsuji-Trost Reaction of Non-Derivatized Allylic Alcohols
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0001-8735-5397
Rekke forfattare: 4
2018 (engelsk)Inngår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, nr 14, s. 3488-3498Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2018. Vol. 24, nr 14, s. 3488-3498
Emneord [en]
asymmetric catalysis, cuspareine, OH activation, palladium, Tsuji-Trost reaction
HSV kategori
Identifikatorer
URN: urn:nbn:se:su:diva-154728DOI: 10.1002/chem.201705164ISI: 000426764400020PubMedID: 29178406OAI: oai:DiVA.org:su-154728DiVA, id: diva2:1195007
Tilgjengelig fra: 2018-04-04 Laget: 2018-04-04 Sist oppdatert: 2018-04-04bibliografisk kontrollert

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Akkarasamiyo, SunisaSawadjoon, SupapornSamec, Joseph S. M.
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