Abstract
We synthesized in a few steps both diastereomers of orthogonally protected β,γ-diamino acids starting from l-phenylalanine or l-tryptophan. These final compounds are interesting building blocks for peptide synthesis and foldamer chemistry. The key step is a Blaise reaction performed under ultrasound conditions.
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References
Baba A, Yasuda M, Nishimoto Y (2014) Zinc enolates. In: Knochel P, Molander GA (eds) The Reformatsky and Blaise Reactions, Comprehensive organic synthesis II, 2nd edn. Elsevier, Amsterdam, pp 523–542
Bouillère F, Guillot R, Kouklovsky C, Alezra V (2011a) Access to β,γ-diamino acids. Application to the synthesis of 3-deoxyaminostatine. Org Biomol Chem 9:394–399
Bouillère F, Thétiot-Laurent S, Kouklovsky C, Alezra V (2011b) Foldamers containing γ-amino acid residues or their analogues: structural features and applications. Amino Acids 41:687–707
Bouillère F, Feytens D, Gori D et al (2012) Constrained [α]/[γ]-peptides: a new stable extended structure in solution without any hydrogen bond and characterized by a fourfold symmetry. Chem Commun 48:1982–1984
Calvisi G, Dell’Uomo N, De Angelis F et al (2003) A practical and stereoconservative synthesis of (R)-3-Amino-4-(trimethylammonio)butanoate [(R)-Aminocarnitine], and its trimethylphosphonium and simple ammonium analogues starting from D-Aspartic acid. Eur J Org Chem 2003:4501–4505
Cativiela C, Díaz-de-Villegas MD (2007) Recent progress on the stereoselective synthesis of acyclic quaternary α-amino acids. Tetrahedron Asymmetry 18:569–623
Chun YS, Xuan Z, Kim JH, Lee S (2013) An expedient and divergent tandem one-pot synthesis of pyrimidin-2,4-diones using the Blaise reaction intermediate. Org Lett 15:3162–3165
Concellón JM, Rodríguez-Solla H, Simal C et al (2009) The addition reaction of samarium enolates and 2-Haloenolates derived from esters, and amides to imines. Totally stereoselective synthesis of enantiopure 3,4-diamino esters or amides. Adv Synth Catal 351:2991–3000
Davies SG, Lee JA, Roberts PM et al (2012) Parallel kinetic resolution of acyclic γ-amino-α, β-unsaturated esters: application to the asymmetric synthesis of 4-Aminopyrrolidin-2-ones. Org Lett 14:218–221
Dénès F, Pérez-Luna A, Chemla F (2010) Addition of metal enolate derivatives to unactivated carbon–carbon multiple bonds. Chem Rev 110:2366–2447
Gomez-Bengoa E, Linden A, López R et al (2008) Asymmetric aza-Henry reaction under phase transfer catalysis: an experimental and theoretical study. J Am Chem Soc 130:7955–7966. doi:10.1021/ja800253z
Guichard G, Huc I (2011) Synthetic foldamers. Chem Commun 47:5933–5941
Hernández JN, Martín VS (2004) First practical protection of α-amino acids as N,N-benzyloxycarbamoyl derivatives. J Org Chem 69:3590–3592
Hoang CT, Alezra V, Guillot R, Kouklovsky C (2007) A stereoselective entry into functionalized 1,2-diamines by zinc-mediated homologation of α-amino acids. Org Lett 9:2521–2524
Hoang CT, Bouillère F, Johannesen S et al (2009) Amino acid homologation by the Blaise reaction: a new entry into nitrogen heterocycles. J Org Chem 74:4177–4187
Juaristi E, Soloshonok V (2005) Enantioselective synthesis of beta-amino acids, 2nd edn. Wiley, New Jersey. ISBN:978-0-471-46738-0
Kim JH, Chun YS, Lee S (2013) Tandem Blaise/retro-Blaise reaction for the nitrile-mediated regioselective intermolecular addition of unstabilized zinc ester enolates (Reformatsky reagents) to 1-alkynes and 1,3-enynes. J Org Chem 78:11483–11493
Martinek TA, Fülöp F (2012) Peptidic foldamers: ramping up diversity. Chem Soc Rev 41:687–702
Ordóñez M, Cativiela C (2007) Stereoselective synthesis of γ-amino acids. Tetrahedron Asymmetry 18:3–99
Pérez-Faginas P, Aranda MT, García-López MT et al (2013) Highly functionalized 1,2–diamino compounds through reductive amination of amino acid-derived β–keto esters. PLoS One 8:e53231
Pilsl L, Reiser O (2011) α/β-Peptide foldamers: state of the art. Amino Acids 41:709–718
Prakash Rao HS, Rafi S, Padmavathy K (2008) The Blaise reaction. Tetrahedron 64:8037–8043
Sakthivel K, Srinivasan K (2014) Synthesis of naphthalene amino esters by the Blaise reaction of o-alkynylarenenitriles. J Org Chem 79:3244–3248
Seebach D, Gardiner J (2008) β-Peptidic peptidomimetics. Acc Chem Res 41:1366–1375
Shinagawa S, Kanamaru T, Harada S et al (1987) Chemistry of emeriamine and its analogs and their inhibitory activity in long-chain fatty acid oxidation. J Med Chem 30:1458–1463
Shioiri T, Irako N (2002) An efficient synthesis of the piperazinone fragment of pseudotheonamide A1 via a stereoselective intramolecular michael ring closure. Chem Lett 31:130–131
Stanovych A, Guillot R, Kouklovsky C et al (2014) β, γ-Diamino acid: an original building block for hybrid α/γ-peptide synthesis with extra hydrogen bond donating group. Amino Acids 46:2753–2757
Thétiot-Laurent S, Bouillère F, Baltaze JP et al (2012) Original β, γ-diamino acid as an inducer of a γ-turn mimic in short peptides. Org Biomol Chem 10:9660–9663
Toniolo C, Crisma M, Formaggio F, Peggion C (2001) Control of peptide conformation by the Thorpe-Ingold effect (Cα-tetrasubstitution). Pept Sci 60:396–419
Vasudev PG, Chatterjee S, Shamala N, Balaram P (2011) Structural chemistry of peptides containing backbone expanded amino acid residues: conformational features of β, γ, and hybrid peptides. Chem Rev 111:657–687
Vogt H, Bräse S (2007) Recent approaches towards the asymmetric synthesis of α, α-disubstituted α-amino acids. Org Biomol Chem 5:406–430
Yoon DH, Ha HJ, Kim BC, Lee WK (2010) Conjugate addition of amines to chiral 3-aziridin-2-yl-acrylates. Tetrahedron Lett 51:2181–2183
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This research was supported by the M.E.S.R. (Doctoral Grant to A.S.).
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Auberger, N., Stanovych, A., Thétiot-Laurent, S. et al. Efficient synthesis of both diastereomers of β,γ-diamino acids from phenylalanine and tryptophan. Amino Acids 48, 2237–2242 (2016). https://doi.org/10.1007/s00726-016-2262-8
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DOI: https://doi.org/10.1007/s00726-016-2262-8