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Brønsted Acid-Catal...
Brønsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
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- Bunrit, Anon (author)
- Uppsala universitet,Institutionen för kemi - BMC
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- Dahlstrand, Christian (author)
- Uppsala universitet,Institutionen för kemi - BMC
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- Olsson, Sandra K. (author)
- Uppsala universitet,Institutionen för kemi - BMC
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- Srifa, Pemikar (author)
- Uppsala universitet,Institutionen för kemi - BMC
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- Huang, Genping (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Orthaber, Andreas (author)
- Uppsala universitet,Molekylär biomimetik
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- Sjöberg, Per J. R. (author)
- Uppsala universitet,Analytisk kemi
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- Biswas, Srijit (author)
- Uppsala universitet,Institutionen för kemi - BMC
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- Himo, Fahmi (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Samec, Joseph S. M. (author)
- Uppsala universitet,Institutionen för kemi - BMC
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(creator_code:org_t)
- 2015-04-01
- 2015
- English.
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 137:14, s. 4646-4649
- Related links:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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https://urn.kb.se/re...
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Abstract
Subject headings
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- 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.
Subject headings
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Keyword
- organisk kemi
- Organic Chemistry
Publication and Content Type
- ref (subject category)
- art (subject category)
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- By the author/editor
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Bunrit, Anon
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Dahlstrand, Chri ...
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Olsson, Sandra K ...
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Srifa, Pemikar
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Huang, Genping
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Orthaber, Andrea ...
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show more...
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Sjöberg, Per J. ...
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Biswas, Srijit
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Himo, Fahmi
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Samec, Joseph S. ...
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- About the subject
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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and Organic Chemistr ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
- Articles in the publication
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Journal of the A ...
- By the university
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Stockholm University
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Uppsala University