The Experts below are selected from a list of 2814 Experts worldwide ranked by ideXlab platform

Dipak S Dalal - One of the best experts on this subject based on the ideXlab platform.

Yogesh A Tayade - One of the best experts on this subject based on the ideXlab platform.

Yogesh B Wagh - One of the best experts on this subject based on the ideXlab platform.

Kenneth N. Raymond - One of the best experts on this subject based on the ideXlab platform.

  • Deconvoluting the Role of Charge in a Supramolecular Catalyst
    2018
    Co-Authors: Cynthia M. Hong, Robert G. Bergman, Kenneth N. Raymond, Mariko Morimoto, Eugene A Kapustin, Nicola Alzakhem, Dean F. Toste
    Abstract:

    We have demonstrated that the microenvironment of a highly anionic Supramolecular Catalyst can mimic the active sites of enzymes and impart rate accelerations of a million-fold or more. However, these microenvironments can be challenging to study, especially in the context of understanding which specific features of the Catalyst are responsible for its high performance. We report here the development of an experimental mechanistic probe consisting of two isostructural Catalysts. When examined in parallel transformations, the behavior of these Catalysts provides insight relevant to the importance of anionic host charge on reactivity. These two Catalysts exhibit similar host-substrate interactions, but feature a significant difference in overall anionic charge (12– and 8–). Within these systems, we compare the effect of constrictive binding in a net neutral aza-Cope rearrangement. We then demonstrate how the magnitude of anionic host charge has an exceptional influence on the reaction rates for a Nazarov cyclization, evidenced by an impressive 680-fold change in reaction rate as a consequence of a 33% reduction in Catalyst charge

  • selective monoterpene like cyclization reactions achieved by water exclusion from reactive intermediates in a Supramolecular Catalyst
    Journal of the American Chemical Society, 2012
    Co-Authors: William M Hartcooper, Robert G. Bergman, Dean F. Toste, Kristen N Clary, Kenneth N. Raymond
    Abstract:

    A polyanionic Supramolecular assembly (1) is shown to catalytically cyclize the monoterpene citronellal and two homologues. In contrast to cyclization in acidic aqueous solution, the hydrophobic interior of 1 prevents the capture of reactive intermediates by water. This effect was also observed in the gold-catalyzed cycloisomerization of an enyne. Due to the steric confinement of the Catalyst’s interior, Prins cyclizations in 1 proceed cleanly both for substrates containing and lacking gem-dimethyl substitution. Encapsulation in 1 consequently imposes a degree of mechanistic control that, similar to enzyme catalysis, is not observed in bulk aqueous solution.

  • High-Turnover Supramolecular Catalysis by a Protected Ruthenium(II) Complex in Aqueous Solution
    Journal of the American Chemical Society, 2011
    Co-Authors: Casey J Brown, Robert G. Bergman, Gregory M. Miller, Miles W. Johnson, Kenneth N. Raymond
    Abstract:

    The design of a Supramolecular Catalyst capable of high-turnover catalysis is reported. A ruthenium(II) Catalyst is incorporated into a water-soluble Supramolecular assembly, imparting the ability to catalyze allyl alcohol isomerization. The Catalyst is protected from decomposition by sequestration inside the host but retains its catalytic activity with scope governed by confinement within the host. This host–guest complex is a uniquely active Supramolecular Catalyst, capable of >1000 turnovers.

  • enantioselective catalysis of the aza cope rearrangement by a chiral Supramolecular assembly
    Journal of the American Chemical Society, 2009
    Co-Authors: Casey J Brown, Robert G. Bergman, Kenneth N. Raymond
    Abstract:

    The chiral Supramolecular Catalyst Ga4L6 [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21−74% and enantiomeric excesses from 6 to 64% at 50 °C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 °C. This is the highest enantioselectivity to date induced by the chiral cavity of a Supramolecular assembly.

Robert G. Bergman - One of the best experts on this subject based on the ideXlab platform.

  • deconvoluting the role of charge in a Supramolecular Catalyst
    Journal of the American Chemical Society, 2018
    Co-Authors: Robert G. Bergman, Cynthia M Hong, Mariko Morimoto, Eugene A Kapustin, Nicola Alzakhem
    Abstract:

    We have demonstrated that the microenvironment of a highly anionic Supramolecular Catalyst can mimic the active sites of enzymes and impart rate accelerations of a million-fold or more. However, these microenvironments can be challenging to study, especially in the context of understanding which specific features of the Catalyst are responsible for its high performance. We report here the development of an experimental mechanistic probe consisting of two isostructural Catalysts. When examined in parallel transformations, the behavior of these Catalysts provides insight relevant to the importance of anionic host charge on reactivity. These two Catalysts exhibit similar host-substrate interactions, but feature a significant difference in overall anionic charge (12– and 8–). Within these systems, we compare the effect of constrictive binding in a net neutral aza-Cope rearrangement. We then demonstrate how the magnitude of anionic host charge has an exceptional influence on the reaction rates for a Nazarov cy...

  • Deconvoluting the Role of Charge in a Supramolecular Catalyst
    2018
    Co-Authors: Cynthia M. Hong, Robert G. Bergman, Kenneth N. Raymond, Mariko Morimoto, Eugene A Kapustin, Nicola Alzakhem, Dean F. Toste
    Abstract:

    We have demonstrated that the microenvironment of a highly anionic Supramolecular Catalyst can mimic the active sites of enzymes and impart rate accelerations of a million-fold or more. However, these microenvironments can be challenging to study, especially in the context of understanding which specific features of the Catalyst are responsible for its high performance. We report here the development of an experimental mechanistic probe consisting of two isostructural Catalysts. When examined in parallel transformations, the behavior of these Catalysts provides insight relevant to the importance of anionic host charge on reactivity. These two Catalysts exhibit similar host-substrate interactions, but feature a significant difference in overall anionic charge (12– and 8–). Within these systems, we compare the effect of constrictive binding in a net neutral aza-Cope rearrangement. We then demonstrate how the magnitude of anionic host charge has an exceptional influence on the reaction rates for a Nazarov cyclization, evidenced by an impressive 680-fold change in reaction rate as a consequence of a 33% reduction in Catalyst charge

  • selective monoterpene like cyclization reactions achieved by water exclusion from reactive intermediates in a Supramolecular Catalyst
    Journal of the American Chemical Society, 2012
    Co-Authors: William M Hartcooper, Robert G. Bergman, Dean F. Toste, Kristen N Clary, Kenneth N. Raymond
    Abstract:

    A polyanionic Supramolecular assembly (1) is shown to catalytically cyclize the monoterpene citronellal and two homologues. In contrast to cyclization in acidic aqueous solution, the hydrophobic interior of 1 prevents the capture of reactive intermediates by water. This effect was also observed in the gold-catalyzed cycloisomerization of an enyne. Due to the steric confinement of the Catalyst’s interior, Prins cyclizations in 1 proceed cleanly both for substrates containing and lacking gem-dimethyl substitution. Encapsulation in 1 consequently imposes a degree of mechanistic control that, similar to enzyme catalysis, is not observed in bulk aqueous solution.

  • High-Turnover Supramolecular Catalysis by a Protected Ruthenium(II) Complex in Aqueous Solution
    Journal of the American Chemical Society, 2011
    Co-Authors: Casey J Brown, Robert G. Bergman, Gregory M. Miller, Miles W. Johnson, Kenneth N. Raymond
    Abstract:

    The design of a Supramolecular Catalyst capable of high-turnover catalysis is reported. A ruthenium(II) Catalyst is incorporated into a water-soluble Supramolecular assembly, imparting the ability to catalyze allyl alcohol isomerization. The Catalyst is protected from decomposition by sequestration inside the host but retains its catalytic activity with scope governed by confinement within the host. This host–guest complex is a uniquely active Supramolecular Catalyst, capable of >1000 turnovers.

  • enantioselective catalysis of the aza cope rearrangement by a chiral Supramolecular assembly
    Journal of the American Chemical Society, 2009
    Co-Authors: Casey J Brown, Robert G. Bergman, Kenneth N. Raymond
    Abstract:

    The chiral Supramolecular Catalyst Ga4L6 [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21−74% and enantiomeric excesses from 6 to 64% at 50 °C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 °C. This is the highest enantioselectivity to date induced by the chiral cavity of a Supramolecular assembly.