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Title: Methyl-ligated tin silsesquioxane catalyzed reactions of glucose

Authors:
; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1359261
Grant/Contract Number:
SC0001004
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 341; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-06 15:25:41; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English

Citation Formats

Brand, Stephen K., Josephson, Tyler R., Labinger, Jay A., Caratzoulas, Stavros, Vlachos, Dionisios G., and Davis, Mark E. Methyl-ligated tin silsesquioxane catalyzed reactions of glucose. United States: N. p., 2016. Web. doi:10.1016/j.jcat.2016.06.013.
Brand, Stephen K., Josephson, Tyler R., Labinger, Jay A., Caratzoulas, Stavros, Vlachos, Dionisios G., & Davis, Mark E. Methyl-ligated tin silsesquioxane catalyzed reactions of glucose. United States. doi:10.1016/j.jcat.2016.06.013.
Brand, Stephen K., Josephson, Tyler R., Labinger, Jay A., Caratzoulas, Stavros, Vlachos, Dionisios G., and Davis, Mark E. 2016. "Methyl-ligated tin silsesquioxane catalyzed reactions of glucose". United States. doi:10.1016/j.jcat.2016.06.013.
@article{osti_1359261,
title = {Methyl-ligated tin silsesquioxane catalyzed reactions of glucose},
author = {Brand, Stephen K. and Josephson, Tyler R. and Labinger, Jay A. and Caratzoulas, Stavros and Vlachos, Dionisios G. and Davis, Mark E.},
abstractNote = {},
doi = {10.1016/j.jcat.2016.06.013},
journal = {Journal of Catalysis},
number = C,
volume = 341,
place = {United States},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jcat.2016.06.013

Citation Metrics:
Cited by: 5works
Citation information provided by
Web of Science

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  • The Hayashi–Ito aldol reaction of methyl isocyanoacetate (MI) and benzaldehydes, a classic homogeneous Au(I)-catalyzed reaction, was studied with heterogenized homogeneous catalysts. Among dendrimer encapsulated nanoparticles (NPs) of Au, Pd, Rh, or Pt loaded in mesoporous supports and the homogeneous analogues, the Au NPs led to the highest yield and highest diastereoselectivity of products in toluene at room temperature. The Au catalyst was stable and was recycled for at least six runs without substantial deactivation. Moreover, larger pore sizes of the support and the use of a hydrophobic solvent led to a high selectivity for the trans diastereomer of the product.more » The activation energy is sensitive to neither the size of Au NPs nor the support. A linear Hammett plot was obtained with a positive slope, suggesting an increased electron density on the carbonyl carbon atom in the rate-limiting step. As a result, IR studies revealed a strong interaction between MI and the gold catalyst, supporting the proposed mechanism, in which rate-limiting step involves an electrophilic attack of the aldehyde on the enolate formed from the deprotonated MI.« less
  • The Hayashi–Ito aldol reaction of methyl isocyanoacetate (MI) and benzaldehydes, a classic homogeneous Au(I)-catalyzed reaction, was studied with heterogenized homogeneous catalysts. Among dendrimer encapsulated nanoparticles (NPs) of Au, Pd, Rh, or Pt loaded in mesoporous supports and the homogeneous analogues, the Au NPs led to the highest yield and highest diastereoselectivity of products in toluene at room temperature. The Au catalyst was stable and was recycled for at least six runs without substantial deactivation. Moreover, larger pore sizes of the support and the use of a hydrophobic solvent led to a high selectivity for the trans diastereomer of the product.more » The activation energy is sensitive to neither the size of Au NPs nor the support. A linear Hammett plot was obtained with a positive slope, suggesting an increased electron density on the carbonyl carbon atom in the rate-limiting step. As a result, IR studies revealed a strong interaction between MI and the gold catalyst, supporting the proposed mechanism, in which rate-limiting step involves an electrophilic attack of the aldehyde on the enolate formed from the deprotonated MI.« less