Using the Ni-[(benzylprolyl)amino]benzophenone complex in the Glaser reaction for the synthesis of bis α-amino acids

Abstract

<p>Enantiomerically enriched (<italic>S</italic>)-α-amino acids were obtained. As the initial complex, the Schiff base Ni(<sc>ii</sc>) complexes were used. The target Ni(<sc>ii</sc>) complexes were disassembled and the amino acids were isolated with excellent enantioselectivities.</p>

New pharmaceuticals approved by FDA in 2020: Small‐molecule drugs derived from amino acids and related compounds

“…In this regard, we would like to stress the growing need in availability and affordability of various tactual types of AAs. Indeed, the interest in the development of synthetic approaches for the preparation of tailor‐made AAs in enantiomerically pure form is currently at an all‐time high 82–135 . Some impressive developments have been made in the area of dynamic kinetic resolution of unprotected AAs, 136–139 a methodology which is best suited for large‐scale production and can rival biocatalytic approaches in affordability and low‐cost structure.…”

Asymmetric organic synthesis with stoichiometric transition metal complexes

“…Furthermore, specialized methodologies for C-H activation in stoichiometric transition metal templates may prove invaluable for selective elaborations of complex organic substrates, as well as to provide fundamental insights relevant to the development of catalytic transformations. [5][6][7][8][9][10][11][12][13][14][15][16]…”

“…The release of the free amino acid, as well as recycling of the chiral ligand in 85% yield, has been demonstrated, although the enantiopurity of the quaternary amino acid was not verified. 5 This methodology has been successfully applied to the construction of amino acids featuring unsaturated functionalities, 8 that are of interest for their biological activities applicable to drug development efforts (Scheme 2). The study is notable for demonstrating the feasibility of Cu-catalyzed oxidative Glaser cross-coupling of terminal alkynes groups present on Ni(II) scaffolds.…”

A Stereoselective Entry to Enantiopure (S)-2-Amino-2-methyl-5-arylpent-4-ynoic Acids and Evaluation of Their Inhibitory Activity against Bacterial Collagenase G

“…Therefore, either a chiral substrate, catalyst or even a chiral auxiliary are required to provide a high asymmetric induction in AA syntheses [12,13]. In this regard, chiral Ni(II) complexes based on chiral ligand-(S)-or (R)-N-(benzylprolyl)aminobenzophenone (BPB) and amino acids introduced by Belokon [14] were developed in the last decades as robust and easily available chiral starting materials for the synthesis of tailor-made AAs [15][16][17][18][19][20][21][22]. While the chiral auxiliary BPB reliably provides an asymmetric induction, a Ni ion organizes a proper geometry simultaneously serving as a protecting group for the Nand O-terminus of an α-AA and increasing the acidity of α-protons in the AA residue [15][16][17][18][19][20][21][22].…”