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Exploring the scope of tandem palladium and isothiourea relay catalysis for the synthesis of α-amino acid derivatives

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Abstract

The scope and limitations of a tandem N-allylation/[2,3]-rearrangementprotocol are investigated through the incorporation of a variety of functionalgroups within an allylic phosphate precursor. This method uses readilyaccessible N,N-dimethylglycine aryl esters and functionalizedallylic phosphates, forming quaternary ammonium salts in situ in the presence of a palladium catalyst. Subsequentenantioselective [2,3]-sigmatropic rearrangement, promoted by the chiralisothiourea tetramisole, generates α-amino acid derivatives with two contiguousstereocenters. The incorporation of electron withdrawing ester and amide groupsgave the best results, furnishing the desired products in moderate to goodyields (29-70%), with low diastereocontrol (typically 60:40 dr) but highenantioselectivity (up to 90:10 er). These results indicate that substrate-catalystinteractions in the proposed transition state are sensitive to the substitutionpattern of the substrates.
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Original languageEnglish
Article number2463
Number of pages13
JournalMolecules
Volume25
Issue number10
DOIs
Publication statusPublished - 25 May 2020

    Research areas

  • Isothiourea, Palladium, Enantioselective catalysis, Amino acids, [2,3]-rearrangement, N-allylation

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