Cyclic hepta-peptide derivative from colonial ascidians, Lissocl

Chemistry: natural resins or derivatives; peptides or proteins; – Peptides of 3 to 100 amino acid residues – Cyclic peptides

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530329, 514 11, 514 16, 514 21, C07K 706, C07K 764

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active

060254661

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to trunkamide A.


BACKGROUND OF THE INVENTION

The genus Lissoclinum of ascidians has proven to be an extremely rich source of novel biologically active natural products. Lissoclinum patella for example has yielded over twenty thiazole-containing cyclic peptides, three highly cytotoxic thiazole-containing macrolides and an antibacterial polyketide lactone (Nat. Prod. Rep., 1994, 11, 355 and earlier reports in the series). Another species, L. bistratum, has been reported to produce cyclic hexapeptides (Tetrahedron, 1992, 48, 341; and J. Org. Chem.(1992, 57, 6671), heptapeptides (Tetrahedron Lett. 1993, 2871) and two extremely toxic spiro ketal amides (see J. Med. Chem., 1989, 32, 1354; Tetrahedron, 1988, 44, 451; and J. Am. Chem. Soc., 1992, 114, 11 10). Lissoclinum (didemnum) voeltzkowi produces antileukemic cyclopentenones (J. Amer. Chem. Soc., 1988, 110, 1308) while L. vareau produces bright red heteroaromatic pigments (J. Org. Chem., 1989, 54, 4256) and a benzopentathiepin which is cytotoxic to human colon tumors (J. Amer. Chem. Soc., 1991, 113, 4709).


SUMMARY OF THE INVENTION

The present invention provides the compound trunkamide A of formula: ##STR2## and pharmaceutically acceptable acid addition salts of Trunkamide A.
The compound of the present invention, Trunkamide A, exhibits antitumor activity against cell lines derived from human tumors. By way of illustration, the compound is active against the cell lines P-388 mouse lymphoma, A-549 human lung carcinoma, HT-29 human colon carcinoma and MEL-28 human melanoma. Accordingly, the present invention further provides a method of treating any mammal affected by a malignant tumor sensitive to Trunkamide A, which comprises administering to the affected individual a therapeutically effective amount of Trunkamide A or a pharmaceutically acceptable acid addition salt of Trunkamide A. The Trunkamide A or salt thereof may be administered in the form of a pharmaceutical composition.
The present invention also relates to pharmaceutical compositions which contain Trunkamide A, or a pharmaceutical acceptable acid addition salt thereof, and a pharmaceutically acceptable carrier, as well as a process for preparation of such compositions.
Examples of pharmaceutical compositions of this invention include any solid (tablets, pills, capsules, granules, etc.) or liquid (solutions, suspensions or emulsions) formulation for oral, topical, parenteral or further mode of administration. They may contain the compound in combination with other pharmacologically active compounds. These compositions may need to be sterile when administered parenterally.
The correct dosage of a pharmaceutical composition comprising Trunkamide A will vary according to the pharmaceutical formulation, the mode of application, and the particular situs, host and bacteria or tumor being treated. Other factors like age, body weight, sex, diet, time of administration, rate of excretion, condition of the host, drug combinations, reaction sensitivities and severity of the disease shall be taken into account. Administration can be carried out continuously or periodically within the maximum tolerated dose.
The present invention further provides a method of synthesis of the new compound trunkamide A. Trunkamide A is a cyclic peptide, and conventional techniques for the preparation of such peptides can be adopted without difficulty. For example, trunkamide A can be regarded as a cyclized form of the linear peptide L-Pro-Tzn.L-Phe-L-Dat-L-Das-L-Ile-L-Ala, where Tzn.Phe is phenylalanine thiazoline, Dat is dimethylallylthreonine, and Das is dimethyallylserine. Illustratively such a linear peptide can be prepared and cyclised in accordance with the following reaction scheme: ##STR3##
In this sequence, the tetrapeptide unit Phe-Pro-Ala-Ileu is prepared with the carboxyl of the Phe protected as a benzyl ester or other suitable group. The Ser-Thr unit is separately prepared with the hydroxy groups protected with readily removable groups, and then reacted with the tetrapeptide. The res

REFERENCES:
Isolation and Structure Determination of Didemnenones, Novel Cytotoxic Metabolites from Tunicates; J. Am. Chem. Soc. 1988, 110, 1308-1309; Niels Lindquist and William Fenical, David F. Sesin and Chris M. Ireland, Gregory D. Van Duyne, Craig J. Forsyth, and Jon Clardy; Jun. 26, 1987.
Novel Cytotoxic Compounds from the Ascidian Lissoclinum bistratum; Bernard M. Degnan, Clifford J. Hawkins, Martin F. Lavin, Elizabeth J. McCaffrey, David L. Parry, and Diane J. Watters; J. Med. Chem. 1989, 32, 1354-1359.
Varamines A and B, New Cytotoxic Thioalkaloids from Lissoclinum vareau; J. Org. Chem, vol. 54, No. 17, 1989; Mar. 3, 1989.
Varacin: A Novel Benzopentathiepin from Lissoclinum vareau That Is Cytotoxic toward a Human Colon Tumor; Bradley S. Davidson, Tadeusz F. Moninski, Louis R. Barrows, and Chris M. Ireland; J. Am. Chem. Soc. 1991, 113, 4709-4710.
Revised Structure of Bistramide A (Bistratene A): Application of a New Program for the Automated Analysis of 2D INADEQUATE Spectra; Mark P. Foster, Charles L. Mayne, Reinhard Dunkel, Ronald J. Pugmire, David M. Grant, Jean-Michel Kornprobst, Jean-Francois Verbist, Jean-Francois Biard, and Chris M. Ireland; J. Am. Chem. Soc. 1992, 114, 1110-1111.
Bistratamides C and D. Two New Oxazole-Containing Cyclic Hexapeptides Isolated from a Phillipine Lissoclinum bistratum Ascidian; Mark P. Foster, Gaseously P. Conception, Gina B. Canaan, and Chris M. Ireland; J. Or. Chem, 1992, 57, 6671-6675.
Proton Nuclear Magnetic Study of Bistramide A., a new cytotoxic drug isolated from Lissoclinum Bistratum Sluiter; D. Gouiffes, S. Moreau, N. Helbecque, J.L. Bernier, J.P. Henichart, Y. Barbin, D. Laurent, J.F. Verbist; Tetrahedron Vo. 44 No. 2, pp. 451 to 159, 1988.
Vycloxazoline: A Cytrotoxic Cyclic Hexapeptide from the Asicidian Lissoclinum Bistratum: Trevor W. hambley, Clifford J. Hawkins, Martin F. Lavin, Anna Van Den Break and Diane J. Waiters; Tetrahedron vol. 48, No. 2, pp. 341-348, 1992.
Nairaiamides A. and B. Two Novel Di-Proline Heptapeptides Isolated from a Figian Lissoclinum bistratum Ascidian Mar. P. Foster and Chris M. Ireland; Tetrahedron Letters, vol. 34, No. 18, pp. 2871-2874, 1993.
Marine Natural Products; D. J. Faulkner; Natural Product Reports, 1993, vol. 10, p. 497.
Carroll, et al., "Patellins 1-6 and Trunkamide A: Novel Cyclic Hexa-, Hepta and Octapeptides from Colnial Ascidians, Lissoclinum sp." Aust. J. Chem, 1996, 49, 659-667.

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