Summary
A novel cyclic dipeptide —cyclo[(S)-His-(S)-NorArg] — has been prepared which catalyzes an enantioselective version of the Strecker amino acid synthesis. The catalyst, when present in 2 mol % quantity in methanol solution, catalyzes the addition of hydrogen cyanide toN-alkylimines to affordα-amino nitriles in high yield and high enantiomeric excess. Furthermore, acid hydrolysis ofN-benzhydryl-α-amino nitriles afforded the correspondingα-amino acids directly. This methodology affords a variety of arylglycines in exceptionally high enantiomeric excess, but aliphatic amino acids were obtained with low enantioselectivity. Current efforts are underway to expand the scope of this reaction, as well as to elucidate the mechanism of catalysis and the roles played by substrate and catalyst in determining the stereochemical outcome of the reaction.
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References
Becker W, Freund H, Pfeil E (1965) Stereospecific synthesis of D-hydroxynitriles and optically active ethanolamines. Angew Chem Int Ed Engl 4: 1079
Chakraborty TK, Reddy GV, Hussain KA (1991) Diastereoselective Strecker synthesis usingα-phenylglycinol as chiral auxiliary. Tetrahedron Lett 32: 7597–7600
Chakraborty TK, Hussain, KA, Reddy GV (1995)α-Phenylglycinol as chiral auxiliary in diastereoselective Strecker synthesis ofα-amino acids. Tetrahedron 51: 9179–9190
Dale JA, Dull DL, Mosher HS (1969)α-Methoxy-α-trifuoromethylphenylacetic acid, a versatile reagent for the determination of enantiomeric composition of alcohols and amines. J Org Chem 34: 2543–2549
Danda H (1991) Essential factors in asymmetric hydrocyanation catalyzed by cyclo(-(R)-Phe-(R)-His-). Synlett: 263–264
Danda H, Nishikawa H, Otaka K (1991) Enantioselective autoinduction in the asymmetric hydrocyanation of 3-phenoxybenzaldehyde catalyzed by cyclo[(R)-phenylalanyl-(R)-histidyl]. J Org Chem 56: 6740–6741
Davis FA, Reddy RE, Portonovo PS (1994) Asymmetric Strecker synthesis using enantiopure sulfinimines: a convenient synthesis ofα-amino acids. Tetrahedron Lett 35: 9351–9354
Davis FA, Portonovo PS, Reddy RE, Chiu Y (1996) Asymmetric Strecker synthesis using enantiopure sulfinimines and diethylaluminum cyanide: the alcohol effect. J Org Chem 61: 440–443
Duthaler RO (1994) Recent developments in the stereoselective synthesis ofα-aminoacids. Tetrahedron 50: 1539–1650
Effenberger F (1994) Synthesis and reactions of optically active cyanohydrins. Angew Chem Int Ed Engl 33: 1555–1564
Ellman J, Mendel D, Anthony-Cahill S, Noren CJ, Schultz PG (1991) Biosynthetic method for introducing unnatural amino acids site-specifically into proteins. Methods Enzymol 20: 301–306
Harada K (1963) Asymmetric synthesis ofα-amino-acids by the Strecker synthesis. Nature 200: 1201
Hruby VJ, Sharma SD (1991) Designing peptide and protein ligands for biological receptors. Curr Opin Biotechnol 2: 599–605
Inaba T, Kzono I, Fujita M, Ogura K (1992) An efficient and practical synthesis of L-α-amino acids using (R)-phenylglycinol as a chiral auxiliary. Bull Chem Soc Jpn 65: 2359–2365
Lapworth J (1903) Reactions involving the addition of hydrogen cyanide to carbon compounds. J Chem Soc 83: 995–1009
Marvell CS, Noyes WA (1920) A study of the possible asymmetry of the aliphatic diazo compounds. J Am Chem Soc 42: 2259–2278
North M (1993) Catalytic asymmetric cyanohydrin synthesis. Synlett: 807–820
Ogata Y, Kawasaki A (1970) Mechanistic aspects of the Strecker aminonitrile synthesis. J Chem Soc (B) 1971: 325–329
Oku J, Inoue S (1981) Asymmetric cyanohydrin synthesis catalyzed by a synthetic cyclic dipeptide. J Chem Soc Chem Commun 1981: 229–230
Patel MS, Worsley M (1969) Asymmetric synthesis of optically activeα-amino acids by hydrocyanic acid addition to the optically active Schiff base. Can J Chem 48: 1881–1884
Phadtare SK, Kamat SK, Panse GT (1985) Asymmetric synthesis ofα-amino acids. Ind J Chem 24B: 811–814
Prelog V, Wilhelm M (1954) Untersuchungen über asymmetrische Synthesen VI). Der Reaktionsmechanismus und der sterische Verlauf der asymmetrischen Cyanhydrin-Synthese. Helv Chim Acta 37: 1634–1660
Scholtz JM, Bartlett PA (1989) A convenient differential protection strategy for functional group manipulation of aspartic and glutamic acids. Synthesis: 542–544
Scott FL, O'Donovan DG, Reilly J (1953) Studies in the pyrazole series. III. Substituted guanidines. J Am Chem Soc 75: 4053–4054
Strecker A (1850) Über die künstlische Bildung der Milchsäure und einen neuen, dem Glycocoll homologen Körper. Liebigs Ann Chem 75: 27–51
Tanaka K, Mori A, Inoue S (1990) The cyclic dipeptide cyclo[(S)-phenylalanyl-(S)-histidyl)] as a catalyst for asymmetric addition of hydrogen cyanide to aldehydes. J Org Chem 55: 181–185
Walia JS, Bannore SN, Walia AS, Guillot L (1974) Mechanism for the formation ofα-aminonitriles: intermediacy of an imine or a cyanohydrin. Chem Lett: 1005–1008
Wallace CJA, Mascagni P, Chait BT, Collawn JF, Paterson Y, Proudfoot AE, Kent SBH (1989) Substitutions engineered by chemical synthesis at three conserved sites in mitochondrial cytochrome c. J Biol Chem 264: 15199–15209
Weinges K, Blackholm H (1980) Herstellung optisch aktiver Aminonitrile. Chem Ber 113: 3098–3102
Williams RM (1989) Synthesis of optically activeα-amino acids. In: Baldwin JE, Magnus PD (eds) Organic chemistry series. Pergamon, Oxford
Williams RM, Hendrix JA (1992) Asymmetric synthesis of arylglycines. Chem Rev 92: 889–917
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A preliminary communication on this work has recently appeared in: Iyer MS, Gigstad KM, Namdev ND, Lipton MA (1996) J Am Chem Soc 118: 4910–4911.
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Iyer, M.S., Gigstad, K.M., Namdev, N.D. et al. Asymmetric catalysis of the Strecker amino acid synthesis by a cyclic dipeptide. Amino Acids 11, 259–268 (1996). https://doi.org/10.1007/BF00807935
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DOI: https://doi.org/10.1007/BF00807935