Resolution/Deracemization of Chiral α-Amino Acids Using Resolving Reagents with Flexible Stereogenic Centers

Soloshonok, Vadim A.; Ellis, Trevor K.; Ueki, Hironobu; Ono, Taizo

doi:10.1021/ja9026055

Cited by 90 publications

(54 citation statements)

References 27 publications

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“…[27,28] The bond lengths of Ni-N are within the normal region. [22,29] The molecular structure (Figure 2 It is proposed that the oxidative addition of the amino N sp3 -H of 1-4 at the nickel(II) atom of NiMe 2 (PMe 3 ) 3 to form a nickel(IV) intermediate A is the first step. [30] The reductive elimination at the unstable nickel(IV) atom occurred between the cis-orientated Ni-Me and Ni-H bonds to afford the tetracoordinate methyl nickel(II) species B with the escape of one methane molecule.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation

Guo

Zhang

Wang

et al. 2015

Zeitschrift anorg allge chemie

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Section: Resultsmentioning

confidence: 99%

Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation

Guo

Zhang

Wang

et al. 2015

Zeitschrift anorg allge chemie

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“…However, when 1 equiv. of base is added to this NMR solution, only one set of imine peaks is formed (20). Here again, the stronger charged H-bond in 20 compared to the corresponding neutral H-bond in 19 allows the highly stereoselective interaction to take place in 20 but not in 19.…”

Section: 2-amino Alcohols and 12-diaminesmentioning

confidence: 99%

Mimicking Nature to Make Unnatural Amino Acids and Chiral Diamines

So¹,

Kim

Mui

et al. 2011

Eur J Org Chem

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Keywords: Amino acids / Amines / Transamination / Rearrangement / Chiral resolution Biomimetic studies of pyridoxal and pyridoxamine models are of both fundamental and practical interest. This review examines (i) deracemization of α-amino acids with a chiral pyridoxal model, (ii) sensing of chirality of small molecules including α-, β-, and γ-amino acids, peptides, amino alcohols and diamines with an achiral pyridoxal model and (iii) stereospecific synthesis of chiral diamines with a chiral pyridoxamine model. A binol-based aldehyde is useful as a chiral pyridoxal model to deracemize a variety of α-amino acids to make D-amino acids. 2,2Ј-Dihydroxybenzophenone is useful

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“…Modular design of these derivatives [140] allowed full rational control over their physicochemical properties, in particular solubility, as well as reactivity [141,142]. Preliminary results demonstrated quite promising potential of these new nucleophilic glycine equivalents for the general synthesis of various a-amino acids via alkyl halide alkylations, aldol and Michael addition reactions [143].…”

Section: Addition Reactionsmentioning

confidence: 99%

Practical Synthesis of Fluorine-Containing α- and β-Amino Acids: Recipes from Kiev, Ukraine

2009

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Naturally occurring compounds containing a C-F bond are extremely rare; only a handful of fluorine-containing carboxylic acids have been described so far. By contrast, man-made fluorine-containing derivatives of all major classes of biologically important compounds are extremely promising medicinal targets used in the elucidation of biochemical, metabolic transformations and the development of new pharmaceuticals. Among the fluorine-containing derivatives of natural products, fluorinated analogs of amino acids are of particular interest and medicinal potential. This article presents a concise review of various synthetic methods, developed by the Kiev's school of bioorganic chemistry, for the preparation of fluorine-containing analogs of α- and β-amino acids, α-hydroxy acids, amines, as well as their phosphorus and sulfur-derived compounds, in enantiomerically pure form. One of the major methodological goals of the study was practicality, which is understood by us as stereochemical generality, operational convenience and synthetic affordance for each reaction step and isolation of the target products. The synthetic methods developed by our group can be roughly divided in two general categories: fluorine-adaptation of known synthetic approaches and discovery of new reactions. The former approach is most prominently represented by asymmetric homologation of nucleophilic glycine equivalents using fluorinated substrates via alkyl halide alkylations, aldol and Michael addition reactions. A plethora of discovered unexpected reaction outcomes, in particular stereochemical, are emphasized in this review and the particular role of fluorine, in altering the 'normal' reaction result, is explained. The latter direction is notably represented by the novel 1,3-proton shift reaction, a biomimetic reductive amination of fluorinated carbonyl compounds to the corresponding amines and amino acids, as well as the development of α-fluoroalkyl epoxides as true fluorinated synthons for generalized asymmetric synthesis of various biologically relevant compounds. Despite the highly anticipated potential of fluorine-containing amino compounds, their medicinal chemistry still remains underexplored. The major obstacle, in our opinion, is that these selectively fluorinated compounds are generally unavailable to the medicinal chemists for comprehensive, systematic study. We hope this review of synthetic methods will highlight and bring attention to particular types of fluorinated amino acids and related compounds readily available on a laboratory scale using methods developed by our group.

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Resolution/Deracemization of Chiral α-Amino Acids Using Resolving Reagents with Flexible Stereogenic Centers

Cited by 90 publications

References 27 publications

Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation

Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation

Mimicking Nature to Make Unnatural Amino Acids and Chiral Diamines

Practical Synthesis of Fluorine-Containing α- and β-Amino Acids: Recipes from Kiev, Ukraine

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Resolution/Deracemization of Chiral α-Amino Acids Using Resolving Reagents with Flexible Stereogenic Centers

Cited by 90 publications

References 27 publications

Synthesis of Dinuclear Nickel Complexes from Dimethyltris­(trimethylphosphine)nickel(II) via N–H Bond Activation

Synthesis of Dinuclear Nickel Complexes from Dimethyltris­(trimethylphosphine)nickel(II) via N–H Bond Activation

Mimicking Nature to Make Unnatural Amino Acids and Chiral Diamines

Practical Synthesis of Fluorine-Containing α- and β-Amino Acids: Recipes from Kiev, Ukraine

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Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation

Synthesis of Dinuclear Nickel Complexes from Dimethyltris(trimethylphosphine)nickel(II) via N–H Bond Activation