Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
2016 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 40, 13408-13414 p.Article in journal (Refereed) Published
A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016. Vol. 138, no 40, 13408-13414 p.
Catalysis, Catalysts, Ions, Isomerization, Isomers, Ketones, Transition metals, Allylic alcohol, Allylic ethers, Base catalyzed, Basic conditions, Computational investigation, Conjugate acid, Electron-deficient, Transition metal catalysts, Ethers
IdentifiersURN: urn:nbn:se:kth:diva-195245DOI: 10.1021/jacs.6b08350ISI: 000385469600048ScopusID: 2-s2.0-84991284118OAI: oai:DiVA.org:kth-195245DiVA: diva2:1047122
FunderSwedish Research CouncilKnut and Alice Wallenberg FoundationVINNOVAWenner-Gren Foundations
QC 201611162016-11-162016-11-022016-11-16Bibliographically approved