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Brønsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
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2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 14, 4646-4649 p.Article in journal (Refereed) Published
Abstract [en]

The hydroxyl group of enantioenriched benzyl, propargyl, allyl, and alkyl alcohols has been intramolecularly displaced by uncharged O-, N-, and S-centered nucleophiles to yield enantioenriched tetrahydrofuran, pyrrolidine, and tetrahydrothiophene derivatives with phosphinic acid catalysis. The five-membered heterocyclic products are generated in good to excellent yields, with high degree of chirality transfer, and water as the only side-product. Racemization experiments show that phosphinic acid does not promote S(N)1 reactivity. Density functional theory calculations corroborate a reaction pathway where the phosphinic acid operates as a bifunctional catalyst in the intramolecular substitution reaction. In this mechanism, the acidic proton of the phosphinic acid protonates the hydroxyl group, enhancing the leaving group ability. Simultaneously, the oxo group of phosphinic acid operates as a base abstracting the nucleophilic proton and thus enhancing the nucleophilicity. This reaction will open up new atom efficient techniques that enable alcohols to be used as nucleofuges in substitution reactions in the future.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015. Vol. 137, no 14, 4646-4649 p.
National Category
Organic Chemistry
URN: urn:nbn:se:su:diva-117729DOI: 10.1021/jacs.5b02013ISI: 000353177100014OAI: diva2:818891
Swedish Research CouncilStiftelsen Olle Engkvist ByggmästareThe Wenner-Gren FoundationGöran Gustafsson Foundation for Research in Natural Sciences and MedicineKnut and Alice Wallenberg Foundation
Available from: 2015-06-09 Created: 2015-06-01 Last updated: 2016-10-12Bibliographically approved

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Huang, GenpingHimo, Fahmi
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