Process for the synthesis of exochelins

Organic compounds -- part of the class 532-570 series – Organic compounds – Unsubstituted hydrocarbyl chain between the ring and the -c-...

Patent

Rate now

  [ 0.00 ] – not rated yet Voters 0   Comments 0

Details

C07D22310

Patent

active

060639199

ABSTRACT:
A process for the synthesis of an Exochelin comprising the steps of generating L-N-[(2-benzyloxy-(benzoyl)] serine or L-N-[2-benzyloxy (benzoyl)] threonine, creating L-N-t-Boc-.epsilon.-hydroxynorleucine and reacting same to produce L-N-Boc-.epsilon.-bromonorleucine trimethylsilylethyl ester, providing a dicarboxylic acid and forming an O-benzyl methyl hydroxamate from the dicarboxylic acid, coupling the O-benzyl methyl hydroxamate with the L-N-Boc-.epsilon.-bromonorleucine trimethylsilylethyl ester to give an L-N.sup.2 -Boc-N.sup.6 -methyl,N.sup.6 -(benzyloxy) lysine 2-trimethylsilylethyl ester which incorporates the dicarboxylic acid as modified above, removing the N-tert-butoxycarbonyl protecting group from the L-N.sup.2 -Boc-N.sup.6 -methyl, N.sup.6 -(benzyloxy) lysine 2-trimethylsilylethyl ester to yield a substituted lysine, and coupling the same with the L-N-[2-benzyloxy (benzoyl) serine or -threonine to yield a 2-trimethyl silylethyl ester of dibenzyl Exochelic acid, transforming the 2-trimethyl silylethyl ester of dibenzyl Exochelic acid to dibenzyl Exochelic acid, preparing benzyl epi-cobactin, forming an ester bond between the dibenzyl Exochelic acid and benzyl epi-cobactin to form an intermediate, and, hydrogenolytically removing three benzyl groups from said intermediate, resulting in the synthesized Exochelin. More particularly, a synthesis for Exochelin 786SM (R) is disclosed wherein the dicarboxylic acid is suberic acid and the serine form is utilized.

REFERENCES:
patent: 5721209 (1998-02-01), Horwitz et al.
patent: 5786326 (1998-07-01), Horwitz
Macham, L.P., Ratledge, C. and Nocton J.C., "Extracellular Iron Acquisition by Mycobacteria: Role of the Exochelins and Evidence Against the Participation of Mycobactin", Infection and Immunity, Dec. 1975, pp. 1242-1251, vol. 12, No. 6.
Barclay, R. and Ratledge, C., "Mycobactins and Exochelins of Mycobacterium tuberculosis, M. bovis, M. africanum and Other Related Species", Journal of General Microbiology, 1988, pp. 134, 771-776.
Machum, L.P. and Ratledge, C., Journal of General Microbiology, 1975, pp. 89, 379-382.
Mauer, P.J. and Miller, J.J. "Total Synthesis of a Mycobactin: Mycobatin S2", 1983, J. Am. Chem. Soc., pp. 240-245, vol. 105.
Mauer, P.J. and Miller, M.J., "Microbial Iron Chelators: Total Synthesis of Aerobactin and Its Constituent Amino Acid, N.sup.6 -Acetyl-N.sup.6 -hydroxylysine" 1982, J. Am. Chem. Soc.104, pp. 3096-3101.
Farkas, L. et al., "The Syntheses of Wightin and Echioidinn, Two Flavones From Andrographis Wightiana", 1967, Tetrahedron,vol. 23, pp. 741-744.
Schniepp, L.E. and Geller, H.H., "Preparation of Dihydropyran .delta.-Hydroxyvaleraldehyde and 1,5-Pentanediol from Tetrahydrofurfuryl Alcohol"1946, J.An, Chem. Soc., vol. 68, pp. 1646-1648.
Gaudry, R., The Synthesis ofD,L-.alpha.-Amino-.epsilon.-Hydroxycaproic Acid and a New Synthesis of D,L-LYSINE.sup.1, Can. J. Res. Sec.B, 1946, vol. 26, pp. 387-392.
Dreyfuss, P, "Synthesis and Some Pharmacological Properties of 8-.epsilon.-Hydroxynorleucine-Vasopressin", J.Med. Chem., 1974, vol. 17(2) , pp. 252-255.
Berlinguet, L. and Gaudry, R Enzymatic Resolution of DL-.alpha.-Amino-.delta.-Hydroxy-n-Valeric Acid, 1952, J.Biol. Chem., vol. 198. pp. 765-769.
Bodanszky, M. et al., 1978 "Cholecystokinin (PNCREOZYMIN). 4..sup.1 Synthesis and Properties of a Biologically Active Analogue of the C-Terminal Heptapetptide with .epsilon.-Hydroxynorlecucine Sulfate Replacing Tyrosine Sulfate"J.Med. Chem. vol. 21(10), pp. 1030-1035.
Maurer, P.J. and Miller, M.J.1981, Mycobactins: Synthesis of (-)-Cobactin T from .epsilon.-Hydroxynorleucine, J. Org. Chem. Soc vol. 46(13), 2835-2836.
Birnbaum, S.M. Levintow, L. Kingsley, R.B. and Greenstein, J.P., "Specificity of Amino Acid Acylases"1952, J.Biol. Chem, , vol. 194, pp. 455-470.
Corey, E. J. and Vankateswarlu, A., "Protection of Hydroxyl Groups as tert-Butyldimethylsilyl Derivatives" 1972, J.Am. Chem. Soc.,vol. 94, pp. 6190-6191.
Sieber, P., "264.Der 2-Trimethylsilylathyl-Rest als selektiv abspaltbare Carboxy-Schutzgruppe.sup.1).sup.2)", 1977, Helv. Chim. Acta, vol. 60, pp. 2711(b)-2716.
Gerlach, H., "298. 2-(Trimethylsilyl) athylester als Carboxylschutzgruppe; Anwendung bei der Synthese des (-)-(S)-Curvularins" 1977, Helv. Chim. Acta, Vol 60, pp. 3039-3044.
Mitsunobu, O., "The Use of Diethyl Azodicarboxylate and Triphenylphosphine in Synthesis and Transformation of Natural Products", 1981, Synthesis, 1981, pp. 1-28.
Hu, J. and Miller, M.J., "Total Synthesis of a Mycobactin a Siderophore and Growth Promoter of Mycobacterium Smegmatis, and Determination of its Growth Inhibitory Activity against Mycobacterium tuberculosis", 1997, pp. 3462-3468, J. Chem. Soc. 119.
Sieglinde Friedrich-Bochnitschek, Herbert Waldmann, and Horst Kunz, Allyl Esters as Carboxy Protecting Groups in the Synthesis of O-Glycopeptides.sup.1, J.Org. Chem, 1989, vol. 54, pp. 751-756.

LandOfFree

Say what you really think

Search LandOfFree.com for the USA inventors and patents. Rate them and share your experience with other people.

Rating

Process for the synthesis of exochelins does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for the synthesis of exochelins, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the synthesis of exochelins will most certainly appreciate the feedback.

Rate now

     

Profile ID: LFUS-PAI-O-259989

  Search
All data on this website is collected from public sources. Our data reflects the most accurate information available at the time of publication.