Browse > Article
http://dx.doi.org/10.14478/ace.2014.1045

Efficient Stereoselective Synthesis of (2S,3S,4S)-3,4-Dihydroxyglutamic Acid  

Jeon, Jongho (Department of Chemical and Biological Engineering, Seoul National University)
Shin, Nara (Department of Chemical and Biological Engineering, Seoul National University)
Lee, Jong Hyup (Department of Chemical and Biological Engineering, Seoul National University)
Kim, Young Gyu (Department of Chemical and Biological Engineering, Seoul National University)
Publication Information
Applied Chemistry for Engineering / v.25, no.4, 2014 , pp. 392-395 More about this Journal
Abstract
(2S,3S,4S)-3,4-Dihydroxyglutamic acid (DHGA), a biologically active ${\alpha},{\beta}$-dihydroxy-${\gamma}$-amino acid, was efficiently synthesized from a readily available D-serine derivative in 30% overall yield over 11 steps. The key stereoselective $OsO_4$-catalyzed dihydroxylation reaction controlled by an N-diphenylmethylene group on the amino group of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (Z)-ester successfully introduced the diol moiety of the intermediate 5a in 86% with more than 10 : 1 diastereomeric ration. Then it was in turn successfully converted to the desired target compound, (2S,3S,4S)-3,4-DHGA, via simple oxidation and hydrolysis in a highly stereoselective manner and a higher yield than the previous syntheses. This result strongly supports that our synthetic methodology of stereoselective $OsO_4$-catalyzed dihydroxylation should be useful in stereoselctive synthesis of various bioactive compounds with an amino diol moiety.
Keywords
(2S,3S,4S)-3,4-DHGA; dihydroxylation; osmium tetroxide; chiral allylic amine;
Citations & Related Records
연도 인용수 순위
  • Reference
1 J. Jeon, J. H. Lee, J.-W. Kim, and Y. G. Kim, syn-Selective dihydroxylation of $\gamma$-amino-$\alpha$,$\beta$-unsaturated (Z)-esters from D-serine: Stereoselective synthesis of D-iminolyxitol, Tetrahedron: Asymmetry, 18, 2448 (2007).   DOI   ScienceOn
2 Taken in part from the Ph.D. thesis; J. Jeon, Stereoselective dihydroxylation reactions of chiral allylic amines and their applications to biologically active natural products, Seoul National University (2008).
3 P. Dauban, C. De Saint-Fuscien, and R. H. Dodd, Application of 2,3-aziridino-$\gamma$-lactone methodology toward the enantiospecific synthesis of the (3S,4S)-isomer of dihydroxy-L-glutamic acid, Tetrahedron, 55, 7589 (1999).   DOI
4 M. Oba, S. Koguchi, and K. Nishiyama, Asymmetric synthesis of 3,4- dihydroxyglutamic acids via enantioselective reduction of cyclic meso-imide, Tetrahedron, 60, 8089 (2004).   DOI
5 H. J. Kim, D. Yoo, S. Y. Choi, Y. K. Chung, and Y. G. Kim, Efficient and stereoselective synthesis for (2S,3S,4S)-3,4-dihydroxyglutamic acid via intramolecular epoxidation, Tetrahedron: Asymmetry, 19, 1965 (2008).   DOI
6 J. S. Oh, D. Y. Park, B. S. Song, J. G. Bae, S. W. Yoon, and Y. G. Kim, anti-Selective dihydroxylation by the ketimine derivatives of the allylic amine in monosubstituted olefins, Tetrahedron Lett., 43, 7209 (2002).   DOI   ScienceOn
7 J. S. Oh, J. Jeon, D. Y. Park, and Y. G. Kim, Stereoselective dihydroxylation reactions of $\gamma$-amino-$\alpha$,$\beta$-unsaturated esters via their aryl ketimine derivatives, Chem. Commun., 770 (2005).
8 J. Jeon, M. Shin, J. W. Yoo, J. S. Oh, J. G. Bae, S. H. Jung, and Y. G. Kim, Highly anti-selective dihydroxylation of 1,2-dialkyl substituted (Z)-allylic amines: Stereoselective synthesis of a D-ribo-phytosphingosine derivative, Tetrahedron Lett., 48, 1105 (2007).   DOI   ScienceOn
9 J. Jeon, S. K. Hong, J. S. Oh, and Y. G. Kim, Stereoselective synthesis of protected (2R,3R,4S)-4,7-diamino-2,3-dihydroxylheptanoic acid: A novel amino acid of callipeltins A and B, J. Org. Chem., 71, 3310 (2006).   DOI   ScienceOn
10 D. W. Choi, Glutamate neurotoxicity and diseases of the nervous system, Neuron, 1, 623 (1988).   DOI   ScienceOn
11 T. Knopfel, R. Kuhn, and H. Allgeier, Metabotropic glutamate receptors: Novel targets for drug development, J. Med. Chem., 38, 1417 (1995).   DOI
12 P. J. Conn and J. P. Pin, Pharmacology and functions of metabotropic glutamate receptors, Annu. Rev. Pharmacol. Toxicol., 37, 205 (1997).   DOI   ScienceOn
13 M. G. Moloney, Excitatory amino acids, Nat. Prod. Rep., 19, 597 (2002).   DOI
14 P. Dauban, A. Chiaroni, C. Riche, and R. H. Dodd, Synthesis of optically pure 3,4-disubstituted L-glutamates from a novel 2,3-aziridino-$\gamma$-lactone 4-carboxylate derivative, J. Org. Chem., 61, 2488 (1996).   DOI
15 N. Langlois, Short stereocontrolled synthesis of (2S,3S,4R)-3,4-dihydroxyglutamic acid, Tetrahedron Lett., 40, 8801 (1999).   DOI   ScienceOn
16 N. Kunishima, Y. Shimada, T. Sato, M. Yamamoto, T. Kumasaka, S. Nakanishi, H. Jingami, and K. Morikawa, Structural basis of glutamate recognition by a dimeric metabotropic glutamate receptor, Natrure, 407, 971 (2000).   DOI   ScienceOn
17 P. Dauban, C. De Saint-Fuscien, F. Acher, L. Prezeau, I. Brabet, J.-P. Pin, and R. H. Dodd, First enantiospecific synthesis of a 3,4-dihydroxy-L-glutamic acid [(3S,4S)-DHGA], a new mGluR1 agonist, Bioorg. Med. Chem. Lett., 10, 129 (2000).   DOI
18 A. I. Virtanene and T. Ettala, Dihydroxyglutamic acid in plants, Acta Chem. Scand., 11, 182 (1957).   DOI
19 A. L. Muller and K. Usheimo, $\beta$,$\gamma$-Dihydroxyglutamic acid III, Acta Chem. Scand., 19, 1987 (1965).   DOI