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Biocatalytic Construction of Quaternary Centers by Aldol Addition of 3,3-Disubstituted 2-Oxoacid Derivatives to Aldehydes

AuthorsMarín-Valls, Roser; Hernández Sánchez, Karel ; Bolte, Michael; Parella, Teodor; Joglar Tamargo, Jesús ; Bujons Vilàs, Jordi ; Clapés Saborit, Pere
KeywordsAldol Addition of 3,3-Disubstituted 2-Oxoacid Derivatives to Aldehydes
Biocatalytic Construction
Quaternary carbons
Issue Date4-Nov-2020
PublisherAmerican Chemical Society
CitationJournal of the American Chemistry Society (2020)
AbstractThe congested nature of quaternary carbons hinders their preparation, most notably when stereocontrol is required. Here we report a biocatalytic method for the creation of quaternary carbon centers with broad substrate scope, leading to different compound classes bearing this structural feature. The key step comprises the aldol addition of 3,3-disubstituted 2-oxoacids to aldehydes catalyzed by metal dependent 3-methyl-2-oxobutanoate hydroxymethyltransferase from E. coli (KPHMT) and variants thereof. The 3,3,3-trisubstituted 2-oxoacids thus produced were converted into 2-oxolactones and 3-hydroxy acids and directly to ulosonic acid derivatives, all bearing gem-dialkyl, gem-cycloalkyl, and spirocyclic quaternary centers. In addition, some of these reactions use a single enantiomer from racemic nucleophiles to afford stereopure quaternary carbons. The notable substrate tolerance and stereocontrol of these enzymes are indicative of their potential for the synthesis of structurally intricate molecules.
Publisher version (URL)https://doi.org/10.1021/jacs.0c09994
Appears in Collections:(IQAC) Artículos
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