Application of Nickel(II) Complexes to the Efficient Synthesis of ?- or ?-Amino Acids

Abstract

Nonproteinogenic α- or β-amino acids have attracted tremendous attention, as they are widely utilized for biological, biochemical, pharmaceutical, and asymmetric chemical investigations. Recently, we developed a series of new strategies for preparing achiral and chiral nickel(ii) complexes for the synthesis of amino acids. We applied these new methods utilizing chiral nickel(ii) complexes for the asymmetric Mannich reaction to synthesize enantiopure α,β-diamino acids, the enantioselective tandem conjugate addition-elimination reaction to prepare glutamic acid derivatives, the Suzuki coupling reaction to yield β(2)-amino acid derivatives, the asymmetric Mannich reaction to synthesize 3-aminoaspartate, the asymmetric Michael addition reaction to give β-substituted-α,γ-diaminobutyric acid derivatives, the asymmetric alkylation reaction to prepare linear ω-trifluoromethyl containing amino acids, and the asymmetric Michael addition reaction to synthesize syn-β-substituted tryptophans.

Preparative Method for Asymmetric Synthesis of (S)-2-Amino-4,4,4-trifluorobutanoic Acid

“…Synthesis of fluorinated AAs is part of a more general field of asymmetric synthesis of tailor-made amino acids. Therefore, some recent advances, covered by the excellent review articles, should be mentioned [52][53][54][55][56][57][58][59][60][61].…”

Optical Resolution of Rimantadine

“…In fact, roughly about one-quarter of recently introduced drugs feature in their structure a residue of tailor-made AA [3,4,5,6]. Accordingly, the research in organic methodology for synthesis of tailor-made AAs is in extremely high demand in nearly every sector of the healthcare industry [7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22]. Our experience with synthesis of tailor-made AAs includes explorations in the areas of fluorine- [23,24,25], phosphorus- [26,27,28], and sulfur-containing AAs [29], as well as sterically constrained [30,31,32] and polyfunctional AA types [33,34,35].…”

Axially chiral Ni(II) complexes of α‐amino acids: Separation of enantiomers and kinetics of racemization

“…[2][3][4][5][6] Subsequently, the development of advanced asymmetric methodologies for scalable synthesis of structurally diverse AAs is currently in high demand. [7][8][9][10][11][12][13][14][15][16][17][18] For quite some time, our groups were interested in pursuing new synthetic approaches for preparation of sterically constrained, 19,20 phosphorus, 21,22 and fluorine-containing [23][24][25] AAs. One of the most methodologically prolific directions, inspired by the seminal work by Belokon, 26,27 has been the chemistry of Ni(II) complexes of AAs derived Schiff bases (Scheme 1).…”