Strategies for the Synthesis of Deoxypropionates

Enantiomerenangereicherte sekundäre Alkyliodide wurden in sekundäre Alkyllithium‐ und Alkylkupferverbindungen unter hoher Retention der Konfiguration überführt. Abfangreaktionen mit unterschiedlichen Elektrophilen, einschließlich chiraler Epoxide, lieferten eine Bandbreite von chiralen Molekülen mit hoher Enantiomerenreinheit (>90 % ee). Diese Methode wurde, ausgehend von kommerziell erhältlichem Ethyl‐(R)‐3‐hydroxybutyrat (>99 % ee), in einer iterativen Weise für die Totalsynthese von (−)‐Lardolure in 13 Stufen und 5.4 % Gesamtausbeute (>99 % ee, dr>99:1) und Siphonarienal in 15 Stufen und 5.6 % Gesamtausbeute (>99 % ee, dr>99:1) angewendet.

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Herstellung enantiomerenangereicherter sekundärer Alkyllithium‐ und Alkylkupferverbindungen – Synthese von (−)‐Lardolure und Siphonarienal

Morozova

Skotnitzki

Moriya

et al. 2018

Angewandte Chemie

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Preparation of Optically Enriched Secondary Alkyllithium and Alkylcopper Reagents—Synthesis of (−)‐Lardolure and Siphonarienal

et al. 2018

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Optically enriched secondary alkyl iodides were converted into secondary alkyllithium and secondary alkylcopper compounds with very high retention of configuration. Quenching with various electrophiles, including chiral epoxides, provided a range of chiral molecules with high enantiomeric purity (>90 % ee). This method has been applied in an iterative fashion in the total synthesis of (-)-lardolure in 13 steps and 5.4 % overall yield (>99 % ee, dr>99:1) and siphonarienal in 15 steps and 5.6 % overall yield (>99 % ee, dr>99:1) starting from commercially available ethyl (R)-3-hydroxybutyrate (>99 % ee).

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Chemoenzymatic Hydroxymethylation of Carboxylic Acids by Tandem Stereodivergent Biocatalytic Aldol Reaction and Chemical Decarboxylation

Marín-Valls¹,

Hernández²,

Bolte

et al. 2019

ACS Catal.

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Chiral 2-substituted 3-hydroxycarboxylic acid derivatives are valuable building blocks for the preparation of naturally occurring and synthetic biologically active molecules. Current methodologies for the preparation of these compounds are still limited for large-scale production due to the high costs, limited microbial strains, low yields, difficult downstream processing, and limited range of structures. We report an effective chemoenzymatic method for the synthesis of enantiomerically pure 2-substituted 3-hydroxycarboxylic esters. The strategy comprises: (i) a stereoselective aldol addition of 2-oxoacids to methanal catalyzed by two enantiocomplementary 2-oxoacid aldolases, (ii) oxidative decarboxylation, and (iii) esterification. Compounds with S-configuration were obtained in 69–80% isolated yields (94–99% ee), and the R enantiomers in 57–88% (88–98% ee), using a substrate concentration range of 0.1–1.0 M. The method developed offers a versatile alternative route to this important class of chiral building blocks and highlights the exciting opportunities available for using natural enzymes with minimal active site modification.

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Strategies for the Synthesis of Deoxypropionates

Cited by 5 publications

References 56 publications

Herstellung enantiomerenangereicherter sekundärer Alkyllithium‐ und Alkylkupferverbindungen – Synthese von (−)‐Lardolure und Siphonarienal

Herstellung enantiomerenangereicherter sekundärer Alkyllithium‐ und Alkylkupferverbindungen – Synthese von (−)‐Lardolure und Siphonarienal

Preparation of Optically Enriched Secondary Alkyllithium and Alkylcopper Reagents—Synthesis of (−)‐Lardolure and Siphonarienal

Chemoenzymatic Hydroxymethylation of Carboxylic Acids by Tandem Stereodivergent Biocatalytic Aldol Reaction and Chemical Decarboxylation

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