Fast and Convenient Synthesis of α-N-Protected Amino Acid Hydrazides

Giancarlo Verardo; Paola Geatti; Barbara Lesa

doi:10.1055/s-2004-837300

PAPER

Fast and Convenient Synthesis of α-N-Protected Amino Acid Hydrazides

Giancarlo Verardo*, Paola Geatti, Barbara Lesa
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Udine, Via del Cotonificio 108, 33100 Udine, Italy
Fax: +39(0432)558803; e-Mail: giancarlo.verardo@uniud.it.;

Abstract

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Abstract

A fast, simple and convenient synthesis of α-N-protected amino acid hydrazides is reported. The procedure involves the reaction between hydrazine monohydrate and the mixed anhydride obtained from an α-N-protected amino acid and ethyl chloroformate. When methylhydrazine was used, the reaction showed a good selectivity, yielding a mixture of 1-acyl-1-methylhydrazine and 1-acyl-2-methylhydrazine in a ratio 87:13. In contrast, when the reaction was carried out with phenylhydrazine, only 1-acyl-2-phenylhydrazine was obtained. No significant difference in reactivity was observed with the different amino acids and N-protection introduced.

Key words

amino acids - hydrazides - regioselectivity - anhydrides - protecting groups

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References

<A NAME="RP11004SS-1">1</A> Klausner YS. Bodanszky M. Synthesis 1974, 549

<A NAME="RP11004SS-2A">2a</A> Milne HB. Kilday W. J. Org. Chem. 1965, 30: 64

<A NAME="RP11004SS-2B">2b</A> Milne HB. Most CF. J. Org. Chem. 1968, 33: 169

<A NAME="RP11004SS-2C">2c</A> Milne HB. Carpenter FH. J. Org. Chem. 1968, 33: 4476

<A NAME="RP11004SS-3A">3a</A> Hofmann K. Magee MZ. Lindenmann A. J. Am. Chem. Soc. 1950, 72: 2814

<A NAME="RP11004SS-3B">3b</A> Hofmann K. Lindenmann A. Magee MZ. Khan NH. J. Am. Chem. Soc. 1952, 74: 470

<A NAME="RP11004SS-3C">3c</A> Gutmann H, Hegedues B, and Zeller P. inventors; Ger. Pat. 1089390. ; Chem. Abstr. 1962, 56, 4860

<A NAME="RP11004SS-3D">3d</A> Schroeder E. Ann. Chem. 1965, 688: 250

<A NAME="RP11004SS-3E">3e</A> Wuensch E. Volk A. Chem. Ber. 1965, 98: 797

<A NAME="RP11004SS-3F">3f</A> Wuensch E. Drees F. Jentsch J. Volk A. Chem. Ber. 1965, 98: 803

<A NAME="RP11004SS-3G">3g</A> Wang Y. Chien S.-C. Lu J.-Y. Huaxue Xuebao 1966, 32: 252 ; Chem. Abstr. 1967, 66, 46577

<A NAME="RP11004SS-3H">3h</A> Poddubnaya NA. Balandina GN. Tambieva OA. Zh. Obshch. Khim. 1971, 41: 436 ; Chem. Abstr. 1971, 75, 20968

<A NAME="RP11004SS-3I">3i</A> Beacham J. Dupuis G. Finn FM. Storey HT. Yanaihara C. Yanaihara N. Hofmann K. J. Am. Chem. Soc. 1971, 93: 5526

<A NAME="RP11004SS-4A">4a</A> Kullmann W. Biochem. Biophys. Res. Commun. 1979, 91: 693

<A NAME="RP11004SS-4B">4b</A> Semenov AN. Lomonosova IV. Berezin VI. Titov MI. Biotechnol. Bioeng. 1993, 42: 1137

<A NAME="RP11004SS-4C">4c</A> Semenov AN. Lomonosova IV. Int. J. Pept. Protein Res. 1994, 43: 113

<A NAME="RP11004SS-5A">5a</A> Dutta AS. Morley JS. J. Chem. Soc., Perkin Trans. 1 1975, 1712

<A NAME="RP11004SS-5B">5b</A> Gante J. Synthesis 1989, 405

<A NAME="RP11004SS-5C">5c</A> Gante J. Angew. Chem., Int. Ed. Engl. 1994, 33: 1699

<A NAME="RP11004SS-5D">5d</A> Venkatraman S. Kong J.-S. Nimkar S. Wang QM. Aubé J. Hanzlik RP. Bioorg. Med. Chem. Lett. 1999, 9: 577

<A NAME="RP11004SS-6A">6a</A> Hegedüs B. Helv. Chim. Acta 1948, 31: 737

<A NAME="RP11004SS-6B">6b</A> Nyman MA. Herbst RM. J. Org. Chem. 1950, 15: 108

<A NAME="RP11004SS-6C">6c</A> Harris JI. Fruton JD. J. Biol. Chem. 1951, 191: 143

<A NAME="RP11004SS-6D">6d</A> Schlögl K. Korger G. Monatsh. 1951, 82: 799

<A NAME="RP11004SS-6E">6e</A> Schlögl K. Derkosch J. Wawersich E. Monatsh. Chem. 1954, 85: 607

<A NAME="RP11004SS-6F">6f</A> Sondheimer E. Holley RW. J. Am. Chem. Soc. 1954, 76: 2816

<A NAME="RP11004SS-6G">6g</A> inventors; Neth. Pat. Appl. 6414901. F. Hoffman La Roche & Co. A.-G; ; Chem. Abstr. 1966, 64, 3685

<A NAME="RP11004SS-6H">6h</A> Tilak MA. Hoffmann JA. J. Org. Chem. 1977, 42: 2098

<A NAME="RP11004SS-6I">6i</A> Moutevelis-Manakakis P. Photaki I. J. Chem. Soc., Perkin Trans. 1 1985, 2277

<A NAME="RP11004SS-7A">7a</A> Radina LB. Khvorova KM. Pushkareva ZV. Zh. Obshch. Khim. 1964, 34: 2140 ; Chem. Abstr. 1964, 61, 9576

<A NAME="RP11004SS-7B">7b</A> Szarvasi E, and Fontaine L. inventors; Ger. Pat. 2200375. ; Chem. Abstr. 1973, 78, 16024

<A NAME="RP11004SS-8">8</A> inventors; ; Brit. Pat. 836332. F. Hoffman La Roche & Co. A.-G. ; Chem. Abstr. 1961, 55, 408

<A NAME="RP11004SS-9">9</A> Jeschkeit H. inventors; Ger. (East) Pat. 59793. ; Chem. Abstr. 1969, 70, 106892

<A NAME="RP11004SS-10A">10a</A> Zahn H. Schnabel E. Ann. 1957, 604: 62

<A NAME="RP11004SS-10B">10b</A> Schroeder E. Ann. Chem. 1965, 681: 231

<A NAME="RP11004SS-10C">10c</A> Fujino M, Shinagawa S, and Kawai K. inventors; Eur. Pat. Appl. 5248. ; Chem. Abstr. 1982, 96, 143328

<A NAME="RP11004SS-10D">10d</A> Fujino M, Shinagawa S, and Kawai K. inventors; U. S. Pat. 4277394. ; Chem. Abstr. 1982, 96, 143328

<A NAME="RP11004SS-11">11</A> Ueda T, Kato S, and Toyoshima S. inventors; Japan Pat. 8070. ; Chem. Abstr. 1958, 52, 13783

<A NAME="RP11004SS-12">12</A> Verardo G. Toniutti N. Gorassini A. Giumanini AG. Eur. J. Org. Chem. 1999, 2943

<A NAME="RP11004SS-13">13</A> Krysin EP. Karel’skii VN. Antonov AA. Rostovskaya GE. Khim. Prir. Soedin. 1979, 684 ; Chem. Abstr. 1981, 94, 175509

<A NAME="RP11004SS-14">14</A> Sham HL. Rosenbrook W. Kati W. Betebenner DA. Wideburg NE. Saldivar A. Plattner JJ. Norbeck DW. J. Chem. Soc., Perkin Trans. 1 1995, 1081

<A NAME="RP11004SS-15">15</A> Cerovsky V. Jost K. Collect. Czech. Chem. Commun. 1985, 50: 878

<A NAME="RP11004SS-16">16</A> Cabezas MJ. del Campo C. Llama E. Sinisterra JV. Gaertner H. J. Mol. Catal. 1992, 71: 261

<A NAME="RP11004SS-17">17</A> Paulus W. Z. Ernaehrungswiss. 1968, 9: 11

<A NAME="RP11004SS-18A">18a</A> Hinman RL. Fulton D. J. Am. Chem. Soc. 1958, 80: 1895

<A NAME="RP11004SS-18B">18b</A> Theuer WJ. Moore JA. J. Org. Chem. 1964, 29: 3734

<A NAME="RP11004SS-18C">18c</A> Condon FE. J. Org. Chem. 1972, 37: 3608

<A NAME="RP11004SS-19A">19a</A> Chen FMF. Benoiton NL. Can. J. Chem. 1987, 65: 1224

<A NAME="RP11004SS-19B">19b</A> Vogel A. In Vogel’s Textbook of Practical Organic Chemistry 5th ed.: Longman Scientific & Technical; New York: 1989. p.762

<A NAME="RP11004SS-19C">19c</A> Vogel A. In Vogel’s Textbook of Practical Organic Chemistry 5th ed.: Longman Scientific & Technical; New York: 1989. p.786