Abstract
A variety of N-carbobenzoxy, N′-formyl gem-diaminoalkyl derivatives have been obtained through Goldsmith-Wick reaction of Z-α-amino acid/peptide acid derived isocyanates with 96% HCOOH in presence of 4-dimethylaminopyridine (DMAP) as catalyst. The reaction proceeds to completion within 2–4 h and results in good yields of the products isolated as stable solids.
Similar content being viewed by others
References
Berman JM, Goodman M (1984) Synthesis of cyclic and acyclic partially modified retro-inverso modified enkaphalins. Int J Pept Prot Res 23:610–620
Chorev M (2005) The partial retro-inverso modification: A road traveled together. Biopolymers (Pept Sci) 80:67–84
Chorev M, Goodman M (1983) Partially modified retro-inverso peptides. Int J Pept Prot Res 21:258–268
Chorev M, Willson CG, Goodman M (1977) A general approach to retro-isomeric linear peptide synthesis. J Am Chem Soc 99:8075–8076
Chorev M, MacDonald SA, Goodman M (1984) Retro-inverso isomerization of peptides: side reactions in the synthesis of N,N'-diacyl-1,1-diamino-2-phenylethane derivatives. J Org Chem 49:821–827
Domling A, Ugi I (2000) Multicomponent reactions with isocyanides. Angew Chem Int Edit 39:3168–3210
Fischer L, Semetey V, Lozano J-M, Schaffner A-P, Briand J-P, Didierjean C, Guichard G, (2007) Succinimidyl carbamate derivatives from N-Protected α-amino acids and dipeptides-Synthesis of ureidopeptides and oligourea/peptide hybrids. Eur J Org Chem 2511–2525
Fletcher MD, Campbell MM (1998) Partially modified retro-inverso peptides: development, synthesis, and conformational behavior. Chem Rev 98:763–796
Fuller WP, Goodman M, Verlander MS (1985) A new class of amino acid based sweeteners. J Am Chem Soc 107:5821–5822
Loudon GM, Almond MR, Jacob JN (1981) Mechanism of hydrolysis of N-(1-aminoalkyl)amides. J Am Chem Soc 103:4508–4515
Pallai PV, Richman S, Struthers RS, Goodman M (1983) Approaches to the synthesis of retro-inverso peptides. Int J Pept Protein Res 21:84–92
Parham ME, Louden GM (1978) Carboxyl-terminal sequential degradation of peptides. Biochem Biophys Res Commun 80:1–6
Patil BS, Vasanthakumar GR, Sureshbabu VV (2003) Isocyanates of Nα-[(9-Fluorenylmethyl)oxy]carbonyl amino acids: synthesis, isolation, characterization, and application to the efficient synthesis of urea peptidomimetics. J Org Chem 68:7274–7280
Sarvari MH, Sharghi H (2006) ZnO as a new catalyst for N-formylation of amines under solvent-free conditions. J Org Chem 71:6652–6654 and reference cited therein
Scheibler L, Chorev M (2003) Synthesis of retroinverso-peptides. In: Goodman M, Felix A, Moroder L, Toniolo C (eds) Methods of organic chemistry (Houben-Weyl): synthesis of peptides and peptidomimetics, vol. E22c. Georg Thieme Verlag Stuttgart, New York, pp 528–551
Schuemacher AC, Hoffmann RW (2001) Condensation between isocyanates and carboxylic acids in the presence of 4-Dimethylaminopyridine (DMAP), a mild and efficient synthesis of amides. Synthesis 243–246
Sudarshan NS, Narendra N, Hemantha HP, Sureshbabu VV (2007) An efficient conversion of the carboxylic group of N-fmoc α-amino acids/peptide acids into N-formamides employing isocyanates as key intermediates. J Org Chem 72:9804–9807
Sureshbabu VV, Kantharaju, Tantry SJ (2005) Curtius rearrangement using ultrasonication: isolation of isocyanates of Fmoc-amino acids and their utility for the synthesis of dipeptidyl ureas. Int J Pept Res Therapeutics 11:131–137
Sureshbabu VV, Patil BS, Venkataramanarao R (2006) Preparation, isolation, and characterization of Nα-Fmoc-peptide isocyanates: solution synthesis of oligo-α-peptidyl ureas. J Org Chem 71:7697–7705
Tantry SJ, Sureshbabu VV (2004) Synthesis of Nα-protected peptide acids by the N→C chain extension employing O, N-bis-trimethylsilyl amino acids using the mixed anhydride method. Indian J Chem 43B:1282–1287
Venkataramanarao R, Sureshbabu VV (2006) Synthesis of retro-inverso peptides employing isocyanates of Nα-Fmoc-amino acids/peptide acids catalyzed by DMAP. Tetrahedron Lett 47:9139–9141
Venkataramanarao R, Sudarshan NS, Sureshbabu VV (2007) Microwave assisted alcoholysis of isocyanates derived from Nα-[(9-fluorenylmethyl)oxy]carbonyl amino acids: synthesis of N-Fmoc-N1-Z-/Boc-/Alloc-/Bsmoc-gem-diamines. Int J Pept Res Therapeutics 13:393–397
Acknowledgements
We are grateful to the Council of Scientific & Industrial Research, Govt. of India for financial support and S.I.F and M.B.U of I.I.Sc., Bangalore for providing NMR and mass facilities.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sureshbabu, V.V., Narendra, N. Synthesis of N-Z, N′-Formyl α-Amino Acid Derived Gem-Diamines. Int J Pept Res Ther 14, 201–207 (2008). https://doi.org/10.1007/s10989-008-9127-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10989-008-9127-2