Asymmetric Synthesis of Tailor-Made Amino Acids Using Chiral Ni(II) Complexes of Schiff Bases. An Update of the Recent Literature

Zou, Yupiao; Han, Jianlin; Saghyan, Ashot S.; Mkrtchyan, Anna F.; Konno, Hiroyuki; Moriwaki, Hiroki; Izawa, Kunisuke; Soloshonok, Vadim A.

doi:10.3390/molecules25122739

Cited by 41 publications

(43 citation statements)

References 126 publications

(199 reference statements)

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“…The absolute configuration of major product (S,2S) was assigned on the basis of spectral and chiroptical properties of 7. [22][23][24][25][26][27] Despite the formation of minor diastereomer (S,2R)-8 in minute amounts, we were able to isolate it in diastereomerically pure form by column chromatography. As expected, major diastereomer (S,2S)- and can be prevented by using inert atmosphere and deoxygenated DMF.…”

Section: Resultsmentioning

confidence: 94%

“…[14][15][16][17][18][19][20][21] Over the last decade, transformations of chiral Ni(II) complexes of Schiff bases derived from tridentate ligands and AAs (Scheme 1) have emerge as a leading methodology for asymmetric synthesis of tailor-made AAs. [22][23][24][25][26][27] Typically, tridentate ligands (S)-1 28,29 are used for preparation of nucleophilic glycine equivalents (S)-2 that serve as the starting templates for incorporation of the desired side-chain(s). Most generally used types of the reactions include alkyl halide alkylations 30,31 aldol, 32 Mannich, 33 and Michael [34][35][36] addition reactions.…”

Section: Introductionmentioning

confidence: 99%

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Asymmetric synthesis of (S)‐α‐(octyl)glycine via alkylation of Ni(II) complex of chiral glycine Schiff base

Takeda

Zou

et al. 2020

Chirality

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Over last decade, the use of Ni(II) complexes, derived from of glycine Schiff bases with chiral tridentate ligands, has emerge as a leading methodology for preparation of structurally diverse Tailor‐Made Amino Acids, the key structural units in modern medicinal chemistry, and drug design. Here, we report asymmetric synthesis of derivatives of (S)‐α‐(octyl)glycine ((S)‐2‐aminodecanoic acid) and its N‐Fmoc derivative via alkylation of chiral nucleophilic glycine equivalent with n‐octyl bromide. Under the optimized conditions, the alkylation proceeds with excellent yield (98.1%) and diastereoselectivity (98.8% de). The observed stereochemical outcome and convenient reaction conditions bode well for application of this method for large‐scale asymmetric synthesis of (S)‐2‐aminodecanoic acid and its derivatives.

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Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Asymmetric synthesis of (S)‐α‐(octyl)glycine via alkylation of Ni(II) complex of chiral glycine Schiff base

Takeda

Zou

et al. 2020

Chirality

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“…In 1985, Belokon and co-workers developed an elegant metal-templated approach for the asymmetric synthesis of enantiopure α-AAs via a chiral Ni(II) complex of the glycine Schiff's base with (S)-BPB (the chiral auxiliary BPB is 2-(N-benzylprolyl) amino benzophenone) and glycine ( Figure 1) [115,116] which later became a general and widely used protocol for the small and large scale production of enantiopure tailor-made α-AAs in academia and industry. [5][6][7][8]13] Later, Belokon group introduced a chiral Ni(II) complex of the dehydroalanine Schiff's base with (S)-BPB -(S)-23 a -as a suitable electrophilic substrate for the conjugate addition with different nucleophiles to yield the corresponding diastereomeric complexes with a very high diastereocontrol. [117][118][119][120][121][122][123] In the subsequent work, the authors applied a chiral dehydroalanine Ni(II) complex (S)-23 a as an olefin type substrate for the conjugate addition of in situ generated radicals providing the β-substituted α-aminopropanoic acid derivatives (S,S)-24 (Scheme 14).…”

Section: Belokon's Chiral Nickel(ii) Complexes Of Dehydroalanine Schimentioning

confidence: 99%

“…Apart from those 20 proteinogenic amino acids, to date, more than 800 natural "unusual" non-proteinogenic AAs and even thousands of synthetic AAs are known in the literature. [1][2][3][4][5][6][7][8][9][10][11][12][13] Non-proteinogenic AAs are of great interest because of their capabilities to modify and fine-tune structures and physicochemical properties of peptides and proteins with the underlying intention to improve their bioactivity and stability. [14][15][16][17][18][19][20][21][22] Moreover, proteinogenic as well as non-proteinogenic AAs are interesting optically active compounds that serve as building blocks in pharmaceutically active compounds.…”

Section: Introductionmentioning

confidence: 99%

Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

2020

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Chiral amino acids (AAs), being the main "building" blocks of the living organisms, are also an important class of organic compounds which broadly applied in synthetic chemistry, biochemistry, catalysis and the designing of new drugs. According to the industrial-commodity market, chiral non-proteinogenic AAs containing various functional groups come to the fore. To date, radical cross-coupling reactions are becoming an option as an attractive powerful tool for AA syntheses. Owing to mild reaction conditions and high functional-group tolerance, radical chemistry represents an ideal strategy for the synthesis of challenging complex non-proteinogenic AAs. Moreover, the radical cross-coupling allows introducing AA residue into drug scaffolds and natural compounds. In the present review, we wish to summarize and discuss all the reported to date methods of the asymmetric synthesis of AAs using radical chemistry by presenting a comprehensive account of the literature in this field going back to 1990. We especially emphasize on a radical chemistry approach and, exclusively, on stereoselective synthesis of various α-, β-, γ-AAs and derivatives employing a different type of radical initiators starting from AIBN and organostannes and ending with powerful photoredox catalysis. Furthermore, the mechanism of the reported reactions will be discussed. Radicals Generated from AA Derivatives in Conjugate Additions 6.1. Radicals Generated from α-Substituted Glycine Derivatives in AA Synthesis 6.2. Modification of Chiral AA Side Chain by Radical Chemistry 7.

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“…NcAAs chemical synthesis continues receiving at present huge attention in the literature due to the relevance of these compounds (Xue et al, 2018;Mei et al, 2020;Zou et al, 2020). On the other hand, the search for sustainable processes to decrease the environmental impact of industrial processes (Wenda et al, 2011;Sheldon and Brady, 2018) is probably the main reason boosting the development of multienzymatic cascade (MEC) reactions.…”

Section: Multienzymatic Cascades For the Production Of Ncaasmentioning

confidence: 99%

Overview on Multienzymatic Cascades for the Production of Non-canonical α-Amino Acids

Martínez‐Rodríguez

Torres

Sánchez

et al. 2020

Front. Bioeng. Biotechnol.

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The 22 genetically encoded amino acids (AAs) present in proteins (the 20 standard AAs together with selenocysteine and pyrrolysine), are commonly referred as proteinogenic AAs in the literature due to their appearance in ribosome-synthetized polypeptides. Beyond the borders of this key set of compounds, the rest of AAs are generally named imprecisely as non-proteinogenic AAs, even when they can also appear in polypeptide chains as a result of post-transductional machinery. Besides their importance as metabolites in life, many of D-α-and L-α-"non-canonical" amino acids (NcAAs) are of interest in the biotechnological and biomedical fields. They have found numerous applications in the discovery of new medicines and antibiotics, drug synthesis, cosmetic, and nutritional compounds, or in the improvement of protein and peptide pharmaceuticals. In addition to the numerous studies dealing with the asymmetric synthesis of NcAAs, many different enzymatic pathways have been reported in the literature allowing for the biosynthesis of NcAAs. Due to the huge heterogeneity of this group of molecules, this review is devoted to provide an overview on different established multienzymatic cascades for the production of non-canonical D-α-and L-α-AAs, supplying neophyte and experienced professionals in this field with different illustrative examples in the literature. Whereas the discovery of new or newly designed enzymes is of great interest, dusting off previous enzymatic methodologies by a "back and to the future" strategy might accelerate the implementation of new or improved multienzymatic cascades.

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Asymmetric Synthesis of Tailor-Made Amino Acids Using Chiral Ni(II) Complexes of Schiff Bases. An Update of the Recent Literature

Cited by 41 publications

References 126 publications

Asymmetric synthesis of (S)‐α‐(octyl)glycine via alkylation of Ni(II) complex of chiral glycine Schiff base

Asymmetric synthesis of (S)‐α‐(octyl)glycine via alkylation of Ni(II) complex of chiral glycine Schiff base

Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

Overview on Multienzymatic Cascades for the Production of Non-canonical α-Amino Acids

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