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Structure-Reactivit...
Structure-Reactivity Relationship Studies for Guanidine-Organocatalyzed Direct Intramolecular Aldolization of Ketoaldehydes
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Ghobril, Cynthia (author)
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- Hammar, Peter (author)
- KTH,Teoretisk kemi
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Kodepelly, Sanjeevarao (author)
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Spiess, Bernard (author)
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Wagner, Alain (author)
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- Himo, Fahmi (author)
- Stockholms universitet,Institutionen för organisk kemi
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Baati, Rachid (author)
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(creator_code:org_t)
- 2010-08-30
- 2010
- English.
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In: ChemCatChem. - : Wiley. - 1867-3880 .- 1867-3899. ; 2:12, s. 1573-1581
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Subject headings
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- Structure-reactivity studies are performed to explore the reaction mechanism of the guanidine-catalyzed intramolecular aldol reaction of ketoaldehydes. A large number of guanidine and guanidine-like catalysts are synthesized and their properties studied. Kinetic profiles and pK(a) values of the catalysts are measured and correlated to reaction barriers calculated using density functional theory (DFT). The DFT calculations show that structural rigidity influences the pKa of the guanidines. Although the basicity is a very important factor in the catalysis, it is not sufficient to fully account for its catalytic efficiency. The availability of two aligned nitrogen reaction sites for proton shuttling in the transition state is an essential feature that helps to rationalize the reactivity pattern and the activation mode for this family of organocatalysts.
Subject headings
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
- NATURVETENSKAP -- Biologi -- Biokemi och molekylärbiologi (hsv//swe)
- NATURAL SCIENCES -- Biological Sciences -- Biochemistry and Molecular Biology (hsv//eng)
Keyword
- aldolization
- density functional calculations
- organocatalysis
- regioselectivity
- structure-activity relationships
- Physical chemistry
- Fysikalisk kemi
- fysikalisk kemi
- Physical Chemistry
- Biochemistry
Publication and Content Type
- ref (subject category)
- art (subject category)
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