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Theoretical Study on the Mechanism of the Petasis‐type Boronic Mannich Reaction of Organoboronic Acids, Amines, and α‐Hydroxy Aldehydes

Theoretical Study on the Mechanism of the Petasis‐type Boronic Mannich Reaction of Organoboronic... The mechanism of a typical Petasis‐type boronic mannich reaction (the styrylboronic acid, dibenzylamine, and α‐hydroxylpropionaldehyde) has been investigated using density functional theory calculations. According to our calculations, the reaction is most likely to proceed through the following steps: 1) the nucleophilic addition of the amine to the aldehyde to form the carbinolamine; 2) the dehydration of the carbinolamine; 3) the formation of the tetra‐coordinated borate intermediate; 4) the CC bond formation by the intramolecular transfer of the styryl group; 5) the hydrolysis of the resulting intermediate to give the final products. The highest point on the energy profile is the transition state for the CC bond formation (118.8 kJ·mol−1 above the reactants in ethanol). Our results can give reasonable explanations on some experimental facts observed for many Petasis‐type boronic Mannich reactions. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chinese Journal of Chemistry Wiley

Theoretical Study on the Mechanism of the Petasis‐type Boronic Mannich Reaction of Organoboronic Acids, Amines, and α‐Hydroxy Aldehydes

Chinese Journal of Chemistry , Volume 28 (1) – Jan 1, 2010

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References (29)

Publisher
Wiley
Copyright
Copyright © 2010 Wiley Subscription Services, Inc., A Wiley Company
ISSN
1001-604X
eISSN
1614-7065
DOI
10.1002/cjoc.201090033
Publisher site
See Article on Publisher Site

Abstract

The mechanism of a typical Petasis‐type boronic mannich reaction (the styrylboronic acid, dibenzylamine, and α‐hydroxylpropionaldehyde) has been investigated using density functional theory calculations. According to our calculations, the reaction is most likely to proceed through the following steps: 1) the nucleophilic addition of the amine to the aldehyde to form the carbinolamine; 2) the dehydration of the carbinolamine; 3) the formation of the tetra‐coordinated borate intermediate; 4) the CC bond formation by the intramolecular transfer of the styryl group; 5) the hydrolysis of the resulting intermediate to give the final products. The highest point on the energy profile is the transition state for the CC bond formation (118.8 kJ·mol−1 above the reactants in ethanol). Our results can give reasonable explanations on some experimental facts observed for many Petasis‐type boronic Mannich reactions.

Journal

Chinese Journal of ChemistryWiley

Published: Jan 1, 2010

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