2024/06/17 by Eric Meggers, Kuan Yin · 7 citations
Biochemistry, Genetics and Molecular Biology · Chemistry · #Amino acid #Asymmetric Hydrogenation and Catalysis #Biochemistry #Chemical Synthesis and Analysis #Chemistry #Combinatorial chemistry #Enzyme Catalysis and Immobilization #Nitrogen #Organic chemistry #Stereochemistry
paper · pdf · doi:10.1055/s-0043-1775371
published in Synthesis 56(17), 2670-2680 (Thieme Medical Publishers (Germany))
openalex publication_date 2024/06/17 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Abstract An improved practical and efficient procedure for the synthesis of non-racemic unnatural α-amino acids through a stereocontrolled rearrangement is reported. Carboxylic acids are converted into azanyl esters RCO2NHBoc followed by an iron-catalyzed 1,3-nitrogen migration to provide non-racemic α-amino acids in an asymmetric (α-monosubstituted α-amino acids) or enantioconvergent fashion (α,α-disubstituted α-amino acids). Under optimized conditions using a fluorinated chiral iron catalyst and 2,2,6,6-tetramethylpiperidine as the base in a solvent mixture of 1,2-dichlorobenzene and CHCl3, enantioselectivities of up to 98% ee were obtained. Such high ee values are important for practical purposes, allowing the direct use of many of the obtained N-Boc-protected α-amino acids for subsequent applications.