Mechanistic investigations in α‐hydroxycarbonyls reduction by BH4‐ |
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Authors: | Simona Marincean Michael Fritz Ryan Scamp James E. Jackson |
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Affiliation: | 1. Department of Natural Sciences, University of Michigan‐ Dearborn, , Dearborn, MI, 48128;2. Department of Chemistry and Biochemistry, University of California‐Los Angeles, , Los Angeles, CA, 90095;3. Department of Chemistry, Michigan State University, , East Lansing, MI, 48824 |
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Abstract: | BH4‐, a well‐known and widely used reducing agent for carbonyl compounds, has been reported to have the ability to participate in dihydrogen bonding, an interaction with applications in catalysis, stereoselectivity and crystal engineering. Specifically, α‐hydroxycarbonyls are activated for reduction by dihydrogen bonding that occurs between BH4‐ and hydroxyl group. We explored the effect of the interaction on the mechanism of these reactions by examining their activation parameters. We found that dihydrogen bonding activates α‐hydroxycyclopentanone for reduction with NBu4BH4 by lowering the activation enthalpy by 6.6 kcal/mol. While the activation entropy is a significant component of the barrier, the changes resulting from the occurrence of dihydrogen bonding are manifested predominantly in the enthalpy term. Computational studies suggest that, while internal hydrogen bonding is allowed by the flexibility of the carbon backbone, that interaction is outweighed by dihydrogen bonding once BH4‐ is present in the system. Experimentally, a red shift of the hydroxyl frequency is observed upon addition of BH4‐ to the reaction mixture, suggesting a dihydrogen bonding interaction. The flexibility of the substrate's skeleton or the selectivity of the hydride sites in BH4‐ does not account for the lack of directing effect of the dihydrogen bonding. When a substrate with a rigid naphthalene backbone moiety, 2‐hydroxyacenaphthylen‐1(2H)‐one, is reduced, the stereochemical outcome is very similar to the one corresponding to the α‐hydroxycyclopentanone. Copyright © 2012 John Wiley & Sons, Ltd. |
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Keywords: | dihydrogen bonding carbonyl activation rate |
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