Chemistry of Pyruvate Enolates: <i>anti</i>‐Selective Direct Aldol Reactions of Pyruvate Ester with Sugar Aldehydes Promoted by a Dinuclear Zinc Catalyst

Molenda, Marta A.; Baś, Sebastian; El‐Sepelgy, Osama; Stefaniak, Matylda; Młynarski, Jacek

doi:10.1002/adsc.201500169

Cited by 11 publications

(3 citation statements)

References 46 publications

(14 reference statements)

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“…25 Solution of 7 (0.7 ml, 0.2M in dry THF) was added to mixture of 3 (0.5 mmol, 1.0 equiv.) and 4 (0.5 mmol, 1.0 equiv.)…”

Section: General Methods For Aldol Reactions Of 3 With 4 Catalyzed By mentioning

confidence: 99%

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Synthesis of 2-Keto-d- and l-gluconic Acid via Stereoselective Direct Aldol Reactions

Baś

Młynarski

2016

J. Org. Chem.

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Stereoselective direct aldol reaction between optically pure d- or l-glyceraldehyde and hydroxyacetylfuran is demonstrated as an efficient and straightforward methodology for the synthesis of six-carbon atom d- and l-arabino-hex-2-ulosonic acids. syn-Selective aldol reactions realized by using either tertiary amines or a dizinc aldol catalyst constitute two parallel routes to the de novo synthesis of orthogonally protected biologically relevant 2-keto-d- and l-gluconic acids.

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“…25 Solution of 7 (0.7 ml, 0.2M in dry THF) was added to mixture of 3 (0.5 mmol, 1.0 equiv.) and 4 (0.5 mmol, 1.0 equiv.)…”

Section: General Methods For Aldol Reactions Of 3 With 4 Catalyzed By mentioning

confidence: 99%

“…The zinc/Prophenol catalyst was prepared as described in literature . A solution of 7 (0.7 mL, 0.2 M in dry THF) was added to a mixture of 3 (0.5 mmol, 1.0 equiv) and 4 (0.5 mmol, 1.0 equiv) in dry THF (1 mL) at −20 °C.…”

Section: Experimental Sectionmentioning

confidence: 99%

Synthesis of 2-Keto-d- and l-gluconic Acid via Stereoselective Direct Aldol Reactions

Baś

Młynarski

2016

J. Org. Chem.

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“…We recently described the efficient aldol reactions of pyruvic esters with chiral aldehydes promoted by Trost's chiral zinc complexes, thus conceptually mimicking type II aldolases . This valuable method was, however, restricted to the synthesis of products with the configuration resulting from the configuration of the starting aldehyde.…”

Section: Introductionmentioning

confidence: 99%

A Concise Organocatalytic Synthesis of 3‐Deoxy‐2‐ulosonic Acids through Cinchona‐Alkaloid‐Promoted Aldol Reactions of Pyruvate

2016

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Direct cross‐aldol reactions of a pyruvate ester with chiral aldehydes, mediated by purely organic catalysts, is described as a crucial step in the synthesis of ulosonic acids. Cinchona alkaloids containing a tertiary amine group efficiently promote direct aldol reactions of a sterically hindered pyruvate ester with various sugar aldehydes. The pyruvic acid ester can be directly used as chemical equivalent of PEP (phosphoenolpyruvate) in imitation of the synthetic principle used in nature. The appropriate combination of a chiral aldehyde with a chiral catalyst allows the flexible preparation of anti‐ or syn‐configured aldols, as desired. As a result, concise syntheses of diverse six‐, seven‐, eight‐, and nine‐carbon ulosonic acid esters are described, by using a biomimetic three‐carbon chain elongation of various sugar aldehydes. Consequently, short and practical syntheses of several ulosonic acids, including three important naturally occurring sugars – 3‐deoxy‐d‐erythro‐hex‐2‐ulosonic acid (KDG), 3‐deoxy‐d‐manno‐oct‐2‐ulosonic acid (KDO), and the rare 3‐deoxyglucosone (3DG), in good overall yields are presented.

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Organocatalytic Activation of Pyruvates Toward Michael Addition to Nitroalkenes: Synthesis of γ‐Aminobutyric Acid (GABA) Derivatives

Włoszczak,

Karczewski,

Mlynarski

2024

Adv Synth Catal

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Despite the significant role of pyruvic acid in biotransformations, the utilization of pyruvates in the field of catalytic asymmetric synthesis has been unexpectedly limited. This statement also applies to enamine catalysis, in which pyruvates seem to be challenging substrates. Recently, the first illustration of the asymmetric addition of pyruvic acid to β‐nitrostyrenes, catalyzed by a NahE enzyme using the enamine mechanism, has appeared in the literature. Now, we demonstrate pyrrolidine‐based catalyst can mimick enamine mechanism used by this enzyme to activate pyruvates in the asymmetric addition to structurally diverse nitroalkenes to produce highly enantioenriched Michael adducts without the limitations in substrate structures associated with biocatalysts. In addition to confirming that optically pure pyrrolidines can serve as ultimately small organic catalysts in pyruvate activation, we present an exceedingly simple and versatile method for the synthesis of optically pure γ‐nitro acids, which are precursors for well‐known active pharmaceutical ingredients namely GABA derivatives

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Chemistry of Pyruvate Enolates: anti‐Selective Direct Aldol Reactions of Pyruvate Ester with Sugar Aldehydes Promoted by a Dinuclear Zinc Catalyst

Cited by 11 publications

References 46 publications

Synthesis of 2-Keto-d- and l-gluconic Acid via Stereoselective Direct Aldol Reactions

Synthesis of 2-Keto-d- and l-gluconic Acid via Stereoselective Direct Aldol Reactions

A Concise Organocatalytic Synthesis of 3‐Deoxy‐2‐ulosonic Acids through Cinchona‐Alkaloid‐Promoted Aldol Reactions of Pyruvate

Organocatalytic Activation of Pyruvates Toward Michael Addition to Nitroalkenes: Synthesis of γ‐Aminobutyric Acid (GABA) Derivatives

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