A new approach to the stereoselective synthesis of conveniently protected α-allyl substituted amino acids; chiral key compounds in the synthesis of constrained peptide isostere constituents

Badorrey, Ramón; Cativiela, Carlos; Dı́az-de-Villegas, Marı́a D.; Gálvez, José A.; Lapeña, Yolanda

doi:10.1016/s0957-4166(96)00516-2

Cited by 33 publications

(7 citation statements)

References 28 publications

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“…The stereoselective chemical synthesis of l ‐(αMe)Nva was performed by extending our general methodology aimed at obtaining C α ‐alkylated α‐amino acids (24). Catalytic hydrogenation of the alkene moiety of (2 S )‐(1 S ,2 R ,4 R )‐10‐(dicyclohexylsulfamoyl)isobornyl‐2‐cyano‐2‐methyl‐4‐pentenoate (19) at 1 atm with palladium on charcoal yielded the saturated pentanoate, the ester moiety of which was subjected to basic hydrolysis leading to the cyanoacid (Fig. 1).…”

Section: Resultsmentioning

confidence: 99%

“…(2 S )‐(1 S ,2 R ,4 R )‐10‐(Dicyclohexylsulfamoyl)isobornyl‐2‐cyano‐2‐methylpentanoate. A solution of (2 S )‐(1 S ,2 R ,4 R )‐10‐(dicyclohexylsulfamoyl)isobornyl‐2‐cyano‐2‐methyl‐4‐pen‐tenoate (19) (518 mg, 1 mmol) in Et 2 O was hydrogenated with 10% palladium on charcoal (50 mg) at room temperature and atmospheric pressure. The reaction was followed by thin‐layer chromatography.…”

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confidence: 99%

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(αMe)Nva: stereoselective syntheses and preferred conformations of selected model peptides

Moretto¹,

Peggion²,

Formaggio³

et al. 2000

The Journal of Peptide Research

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Using different stereoselective chemical and chemoenzymatic approaches we synthesized the chiral, Calpha-methylated alpha-amino acid L-(alphaMe)Nva with a short, linear side-chain. A set of terminally protected model peptides to the pentamer level containing either (alphaMe)Nva or Nva in combination with Ala and/or Aib was prepared using solution methods and characterized fully. Two (alphaMe)Nva peptides were also synthesized using side-chain hydrogenation of the corresponding Calpha-methyl, Calpha-allylglycine (Mag) peptides. A detailed solution and crystal-state conformational analysis based on FT-IR absorption, 1H NMR and X-ray diffraction techniques allowed us to define that: (i) (alphaMe)Nva is an effective beta-turn and 3(10)-helix former; and (ii) the relationship between (alphaMe)Nva chirality and the screw sense of the turn/helix formed is that typical of protein amino acids, i.e. L-(alphaMe)Nva induces the preferential formation of right-handed folded structures. In more general terms, this study reinforced previous conclusions that peptides based on alpha-amino acids with a Calpha-methyl substituent and a Calpha-linear alkyl substituent are characterized by a strong tendency to fold into turn and helical structures.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

(αMe)Nva: stereoselective syntheses and preferred conformations of selected model peptides

Moretto¹,

Peggion²,

Formaggio³

et al. 2000

The Journal of Peptide Research

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“…anol. [115] [116] In a procedure devised by Katsuki, the chiral trans-2,5-bis(methoxymethoxymethyl)pyrrolidine moiety accounts for high diastereoselectivity in the alkylation of the Li am-3.3 Chiral β 2,2,3 -Amino Acids ide enolates [117] derived from α-cyanoalkanoic acid (Scheme 14). [113] The chiral auxiliary was cleaved by treatment with This kind of β-amino acid can be prepared either through α-branched β-amino acid precursors or intermediates, or 6  HCl to give α,α-disubstituted α-cyanoacetic acid, which could be transformed into the corresponding β 2,2 -amino alternatively by a variety of Mannich-type reactions.…”

Section: Chiral β 22 -Amino Acidsmentioning

confidence: 99%

Preparation of Achiral and of Enantiopure Geminally Disubstituted β-Amino Acids for β-Peptide Synthesis

2000

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“…Enantiopure ( S )- 1 used in the present work has been obtained via an economically attractive and generally applicable chemoenzymatic approach developed by DSM Research . However, other stereoselective syntheses of 1 have been reported …”

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confidence: 99%

Stereoselective Iodocyclization of (S)-Allylalanine Derivatives: γ-Lactone vs Cyclic Carbamate Formation

et al. 2007

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An efficient procedure for highly chemo- and stereoselective cyclization of (S)-allylalanine derivatives is reported (diastereomeric ratios up to 96:4) where the reaction course can be completely controlled by switching from gamma-lactones to cyclic carbamates simply with the proper choice of the amino acid protecting groups. Both processes are stereoconvergent and afford the (S,S)-products in high yields, short reaction times, and mild reaction conditions.

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A new approach to the stereoselective synthesis of conveniently protected α-allyl substituted amino acids; chiral key compounds in the synthesis of constrained peptide isostere constituents

Cited by 33 publications

References 28 publications

(αMe)Nva: stereoselective syntheses and preferred conformations of selected model peptides

(αMe)Nva: stereoselective syntheses and preferred conformations of selected model peptides

Preparation of Achiral and of Enantiopure Geminally Disubstituted β-Amino Acids for β-Peptide Synthesis

Stereoselective Iodocyclization of (S)-Allylalanine Derivatives: γ-Lactone vs Cyclic Carbamate Formation

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