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Vadim A Soloshonok - One of the best experts on this subject based on the ideXlab platform.

  • biomimetic reductive amination under the continuous Flow Reaction conditions
    Journal of Fluorine Chemistry, 2010
    Co-Authors: Vadim A Soloshonok, Hector T Catt, Taizo Ono
    Abstract:

    This study present a full account of continuous-Flow Reaction conditions for biomimetic reductive amination of fluorinated carbonyl compounds to corresponding amines and amino acids of biomedical importance. We demonstrate that simple silica-adsorbed DBU can be used as efficient catalysts for on-column 1,3-proton shift Reaction, a key transformation in the biomimetic reductive amination process. This new on-column process features operationally convenient conditions, higher chemical yields, enantioselectivity and purity of the corresponding products as compared with traditional in-flask Reactions. Moreover the removal of base-catalyst, the most delicate problem of the in-flask Reactions, is not an issue in the on-column process, as the silica-adsorbed DBU or polymer-bound guanidine remains on the column and can be reused. This feature renders the overall process substantially more economical and synthetically efficient, in particular, for large-scale synthesis of the corresponding fluorinated amines and amino acids target.

  • continuous Flow asymmetric biomimetic transamination
    Journal of Fluorine Chemistry, 2009
    Co-Authors: Vadim A Soloshonok, Hector T Catt, Taizo Ono
    Abstract:

    This study has demonstrated that conceptually new continuous-Flow Reaction procedure for biomimetic transamination of perfluoroalkyl-containing ketones is substantially more efficient as compared with conventional in-flask approach, allowing preparation of the target fluorinated amines with generally improved chemical yields and enantioselectivity.

  • first example of continuous Flow Reaction conditions for biomimetic reductive amination of fluorine containing carbonyl compounds
    Journal of Fluorine Chemistry, 2008
    Co-Authors: Vadim A Soloshonok
    Abstract:

    Abstract This study presents the first example of continuous-Flow Reaction conditions for biomimetic reductive amination of fluorinated carbonyl compounds using silica-adsorbed DBU as catalyst for on-column process. This new on-column process features operationally convenient conditions, higher chemical yields and purity of products as compared with traditional in-flask Reactions. Furthermore the removal of base-catalyst is not an issue in this process at all, as the catalyst (DBU) remains on the column in the “Reaction zone”, the feature which makes the overall process substantially more efficient and inexpensive, in particular, for large-scale synthesis of the target α-perfluoroalkyl amines.

Taizo Ono - One of the best experts on this subject based on the ideXlab platform.

  • biomimetic reductive amination under the continuous Flow Reaction conditions
    Journal of Fluorine Chemistry, 2010
    Co-Authors: Vadim A Soloshonok, Hector T Catt, Taizo Ono
    Abstract:

    This study present a full account of continuous-Flow Reaction conditions for biomimetic reductive amination of fluorinated carbonyl compounds to corresponding amines and amino acids of biomedical importance. We demonstrate that simple silica-adsorbed DBU can be used as efficient catalysts for on-column 1,3-proton shift Reaction, a key transformation in the biomimetic reductive amination process. This new on-column process features operationally convenient conditions, higher chemical yields, enantioselectivity and purity of the corresponding products as compared with traditional in-flask Reactions. Moreover the removal of base-catalyst, the most delicate problem of the in-flask Reactions, is not an issue in the on-column process, as the silica-adsorbed DBU or polymer-bound guanidine remains on the column and can be reused. This feature renders the overall process substantially more economical and synthetically efficient, in particular, for large-scale synthesis of the corresponding fluorinated amines and amino acids target.

  • continuous Flow asymmetric biomimetic transamination
    Journal of Fluorine Chemistry, 2009
    Co-Authors: Vadim A Soloshonok, Hector T Catt, Taizo Ono
    Abstract:

    This study has demonstrated that conceptually new continuous-Flow Reaction procedure for biomimetic transamination of perfluoroalkyl-containing ketones is substantially more efficient as compared with conventional in-flask approach, allowing preparation of the target fluorinated amines with generally improved chemical yields and enantioselectivity.

Shengzhong Frank Liu - One of the best experts on this subject based on the ideXlab platform.

Masakatsu Shibasaki - One of the best experts on this subject based on the ideXlab platform.

  • anti selective catalytic asymmetric nitroaldol Reaction of α keto esters intriguing solvent effect Flow Reaction and synthesis of active pharmaceutical ingredients
    Journal of the American Chemical Society, 2018
    Co-Authors: Tomoya Karasawa, Naoya Kumagai, Raphael Oriez, Masakatsu Shibasaki
    Abstract:

    A rare-earth metal/alkali metal bimetallic catalyst proved particularly effective for enantioselectively coupling nitroalkanes and α-keto esters in an anti-selective manner to afford synthetically versatile, densely functionalized, and optically active α-nitro tertiary alcohols. A chiral diamide ligand captured two distinct metal cations, giving rise to a catalytically competent solid-phase heterobimetallic catalyst by simple mixing via self-assembly. The advantage of the solid-phase asymmetric catalyst was realized by successful application to the enantio- and diastereoselective Reaction in a continuous-Flow platform. The use of closely related solvents in terms of structures and polarity parameters, THF and its methylated congener 2-Me-THF, had an unexpectedly large solvent effect both on the Reaction rate and the stereoselectivity. The nitroaldol products share a privileged unit for active pharmaceutical ingredients, as demonstrated by the streamlined enantioselective synthesis of the marketed antifungal agents efinaconazole and albaconazole.

  • anti selective catalytic asymmetric nitroaldol Reaction of α keto esters intriguing solvent effect Flow Reaction and synthesis of active pharmaceutical ingredients
    Journal of the American Chemical Society, 2018
    Co-Authors: Tomoya Karasawa, Naoya Kumagai, Raphael Oriez, Masakatsu Shibasaki
    Abstract:

    A rare-earth metal/alkali metal bimetallic catalyst proved particularly effective for enantioselectively coupling nitroalkanes and α-keto esters in an anti-selective manner to afford synthetically versatile, densely functionalized, and optically active α-nitro tertiary alcohols. A chiral diamide ligand captured two distinct metal cations, giving rise to a catalytically competent solid-phase heterobimetallic catalyst by simple mixing via self-assembly. The advantage of the solid-phase asymmetric catalyst was realized by successful application to the enantio- and diastereoselective Reaction in a continuous-Flow platform. The use of closely related solvents in terms of structures and polarity parameters, THF and its methylated congener 2-Me-THF, had an unexpectedly large solvent effect both on the Reaction rate and the stereoselectivity. The nitroaldol products share a privileged unit for active pharmaceutical ingredients, as demonstrated by the streamlined enantioselective synthesis of the marketed antifung...

  • asymmetric Flow catalysis mix and go solid phase nd na catalyst for expeditious enantioselective access to a key intermediate of azd7594
    Tetrahedron, 2017
    Co-Authors: Akihito Nonoyama, Naoya Kumagai, Masakatsu Shibasaki
    Abstract:

    Abstract An anti-selective catalytic asymmetric nitroaldol Reaction was implemented in a continuous-Flow Reaction platform for the synthesis of a key intermediate of a drug candidate. The requisite solid-phase catalyst was readily prepared by mixing an amide-based chiral ligand and inexpensive inorganic salts, NdCl3•6H2O and NaOtBu, without covalent bond linkages. The Flow system was operated with 2-Me-THF as the eluent for ca. 400 h to provide a crude nitroaldol adduct in a highly stereoselective manner with no work-up procedure, reaching turnover number over 1600. Facile reduction of the nitro group of the product afforded a key intermediate of AZD7594, a therapeutic candidate for asthma and chronic obstructive pulmonary disease.

Sunwoo Lee - One of the best experts on this subject based on the ideXlab platform.