Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 31, Pages 7074-7082Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201905708
Keywords
amino acids; diastereoselectivity; electrochemistry; noncovalent interactions; stereoinductors
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Funding
- Russian Foundation for Basic Research [19-29-08012]
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The results of extended comparative investigation of nickel(II) Schiff base complexes (containing various auxiliary chiral moieties) commonly used as a methodological platform for the asymmetric synthesis of tailor-made alpha-amino acids are provided. The following issues are addressed: 1) redox activity (determining the possibility for electrochemically induced reactions); 2) quantitative estimation of the reactivity of deprotonated complexes towards electrophiles; and 3) quantum-chemical estimation of noncovalent interactions in the metal coordination environment (which shed light on the origin of the stereochemical outcome observed for different stereoinductors). Possible mechanisms that determine the relationship between the stereochemical configuration of a molecule and its electronic structure are discussed. The DFT-calculated HOMO-LUMO energies and localization, as well as relative energies for the (S)- and (R)-alanine derivatives, that determine the stereoinduction efficiency in thermodynamically controlled reactions in nickel(II) coordination are provided. The computational data are supported by experimental results on the monobenzylation of glycine derivatives.
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