An Efficient Method for the Synthesis of Enantiopure ω-Amino Acids with Proteinogenic Side Chains

Caterina  Noula; Vassilios  Loukas; George  Kokotos

doi:10.1055/s-2002-33647

PAPER

An Efficient Method for the Synthesis of Enantiopure ω-Amino Acids with Proteinogenic Side Chains

Caterina Noula, Vassilios Loukas, George Kokotos*
Laboratory of Organic Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis, Athens 15771, Greece
Fax: +30(107)274761; e-Mail: gkokotos@cc.uoa.gr;

Abstract

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Abstract

An efficient method for the synthesis of enantiopure ω-amino acids with proteinogenic side chains, starting from the corresponding natural α-amino acids, was developed. N-Protected amino aldehydes, obtained from the corresponding amino alcohols by oxidation with NaOCl in the presence of 4-acetamido-2,2,6,6-tetramethylpiperidine-1-yloxy free radical (AcNH-TEMPO), reacted with the ylides generated from TrO(CH₂)_nP⁺Ph₃I^-. Catalytic hydrogenation produced N-protected ω-amino alcohols. Boc-Protected ω-amino acids were obtained in high yields by the oxidation of these alcohols using NaOCl in the presence of a catalytic amount of AcNH-TEMPO and Bu₄N⁺HSO₄ ^-. The present route to ω-amino acids permits the insertion of any chain length between the amino and carboxy functionalities depending on the chain length of the starting ylide used for the Wittig olefination reaction.

Key words

amino acids - amino alcohols - amino aldehydes - Wittig reactions - ylides

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References

<A NAME="RT01702SS-1A">1a</A> Giannis A. Kolter T. Angew. Chem., Int. Ed. Engl. 1993, 32: 1244

<A NAME="RT01702SS-1B">1b</A> Gante J. Angew. Chem., Int. Ed. Engl. 1994, 33: 1699

<A NAME="RT01702SS-1C">1c</A> Kokotos G. Martin V. Constantinou-Kokotou V. Gibbons WA. Amino Acids 1996, 11: 329

<A NAME="RT01702SS-2A">2a</A> Williams RH. In The Synthesis of Optically Active α-Amino Acids Pergamon; New York: 1989.

<A NAME="RT01702SS-2B">2b</A> Duthaler RO. Tetrahedron 1994, 50: 1539

<A NAME="RT01702SS-2C">2c</A> Rutjes FPJT. Wolf LB. Schoemaker HE. J. Chem. Soc., Perkin Trans. 1 2000, 4197

<A NAME="RT01702SS-3">3</A> Seebach D. Matthews JL. Chem. Commun. 1997, 2015

<A NAME="RT01702SS-4">4</A> Hintermann T. Gademann K. Jaun B. Seebach D. Helv. Chim. Acta 1998, 81: 983

<A NAME="RT01702SS-5">5</A> Gellman SH. Acc. Chem. Res. 1998, 31: 173

<A NAME="RT01702SS-6">6</A> Hanessian S. Yang H. Schaum R. J. Am. Chem. Soc. 1996, 118: 2507

<A NAME="RT01702SS-7">7</A> Hanessian S. Luo X. Schaum R. Michnick S. J. Am. Chem. Soc. 1998, 120: 8569

<A NAME="RT01702SS-8">8</A> Frackenpohl J. Arvidsson PI. Schreiber JV. Seebach D. ChemBioChem 2001, 2: 445

<A NAME="RT01702SS-9A">9a</A> Juaristi E. Enantioselective Synthesis of β-Amino Acids Wiley-VCH; New York: 1997.

<A NAME="RT01702SS-9B">9b</A> Juaristy E. Lopez-Ruiz H. Curr. Med. Chem. 1999, 6: 983

<A NAME="RT01702SS-10">10</A> El Marini A. Roumenstat ML. Viallefont P. Razafindramboa D. Bonato M. Follet M. Synthesis 1992, 1104

<A NAME="RT01702SS-11">11</A> Hanessian S. Schaum R. Tetrahedron Lett. 1997, 38: 163

<A NAME="RT01702SS-12">12</A> Smrcina M. Majer P. Majerová E. Guerassina TA. Eissenstat MA. Tetrahedron 1997, 53: 12867

<A NAME="RT01702SS-13">13</A> Kokotos G. Synthesis 1990, 299

<A NAME="RT01702SS-14">14</A> Kokotos G. Noula C. J. Org. Chem. 1996, 61: 6994

<A NAME="RT01702SS-15">15</A> Jurczak J. Golebiowski A. Chem. Rev. 1989, 89: 149

<A NAME="RT01702SS-16">16</A> Kokotos G. Markidis T. Constantinou-Kokotou V. Synthesis 1996, 1223

<A NAME="RT01702SS-17">17</A> Falkiewicz B. Koodziejczyk AS. Liberek B. Winiewski K. Tetrahedron 2001, 57: 7909

<A NAME="RT01702SS-18">18</A> Walfred SS. Thorsten EF. Synthesis 1990, 453

<A NAME="RT01702SS-19">19</A> Franciotti M. Mordini A. Taddei M. Synlett 1992, 137

<A NAME="RT01702SS-20">20</A> Jurczak J. Kobrzycka E. Gruza H. Prokopowicz P. Tetrahedron 1998, 54: 6051

<A NAME="RT01702SS-21A">21a</A> Leanna MR. Sowin TJ. Morton HE. Tetrahedron Lett. 1992, 33: 5029

<A NAME="RT01702SS-21B">21b</A> Ma Z. Bobbitt JM. J. Org. Chem. 1991, 56: 6110

<A NAME="RT01702SS-22">22</A> Maryanoff BE. Reitz AB. Duhl-Emswiler BA. J. Am. Chem. Soc. 1985, 107: 217

<A NAME="RT01702SS-23A">23a</A> Leznoff CC. Wong JY. Can. J. Chem. 1972, 50: 2892

<A NAME="RT01702SS-23B">23b</A> Kaats-Richters VEM. Zwikker JM. Keegstra EMD. Jenneskens LW. Synth. Commun. 1994, 24: 2399

<A NAME="RT01702SS-24A">24a</A> Schlosser M. Schaub B. de Oliveira-Neto J. Jeganathan S. Chimia 1986, 40: 244

<A NAME="RT01702SS-24B">24b</A> Maryanoff BE. Reitz AB. Chem. Rev. 1989, 89: 863

<A NAME="RT01702SS-25">25</A> Marcovici-Mizrahi D. Gottlieb HE. Marks V. Nudelman A. J. Org. Chem. 1996, 61: 8402

<A NAME="RT01702SS-26">26</A> Dale JA. Dull DL. Mosher H. J. Org. Chem. 1969, 34: 2543