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Mechanism of Asymme...
Mechanism of Asymmetric Homologation of Alkenylboronic Acids with CF3-Diazomethane via Borotropic Rearrangement
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- Biosca, Maria (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Szabó, Kálmán J. (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Himo, Fahmi, 1973- (author)
- Stockholms universitet,Institutionen för organisk kemi
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(creator_code:org_t)
- 2024
- 2024
- English.
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In: Journal of Organic Chemistry. - 0022-3263 .- 1520-6904. ; 89:7, s. 4538-4548
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https://doi.org/10.1...
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Abstract
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- Density functional theory calculations have been performed to investigate the mechanism for the BINOL-catalyzed asymmetric homologation of alkenylboronic acids with CF3-diazomethane. The reaction proceeds via a chiral BINOL ester of the alkenylboronic acid substrate. The calculations reveal a complex scenario for the formation of the chiral BINOL-alkenylboronate species, which is the key intermediate in the catalytic process. The aliphatic alcohol additive plays an important role in the reaction. This study provides a rationalization of the stereoinduction step of the reaction, and the enantioselectivity is mainly attributed to the steric repulsion between the CF3 group of the diazomethane reagent and the γ-substituent of the BINOL catalyst. The complex potential energy surface obtained by the calculations is analyzed by means of microkinetic simulations.
Subject headings
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Publication and Content Type
- ref (subject category)
- art (subject category)
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