Process for the preparation of immunostimulating swainsonine ana

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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536 174, 546 94, C07D47104

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054668093

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BRIEF SUMMARY
FIELD OF INVENTION

The invention relates to processes for the production of swainsonine analogs known in general terms as indolizidine compounds and products thereof.
Swainsonine, 1, (the general structure of which is presented in FIG. 1) is an alkaloid of molecular weight 173.1 which may be derived from both natural and synthetic sources. Swainsonine is a competitive inhibitor of Golgi alpha-mannosidase II (Molyneux, R. J. et al., Science (Wash. D.C.) 216:190 (1981); Tulsiani, D. R. P. et al., J. Biol. Chem. 257:7936 (1982)), an enzyme important in the oligosaccharide processing pathway leading to the synthesis of complex membrane oligosaccharides and secreted glycoproteins. This action, as well as the immunomodulatory effects of swainsonine, accounts in part for antimetastatic and antineoplastic activity in murine tumor model systems. Swainsonine has also been shown to mediate a diverse array of effects, which include inhibition of tumor growth (Dennis et al., J. Nat'l. Cancer Inst., 81:1028 (1989)) and metastasis (White et al., Anticancer Res., 10:1515 (1990)), synergistic with poly-IC and interleukin-2 (J. W. Dennis, Mt. Sinai Hospital, European Patent Application 87308605.2); augmentation of natural killer (Inamura et al., J. Antibiot. Tokyo, 38:936 (1985)) and macrophage (Newton et al., Cancer Commun., 1:373 (1989)) tumoricidal activity; induction of cytokine synthesis and secretion (Newton et al., Cancer Commun., 1:373 (1989)); enhancement in expression of lak (Newton et al., Cancer Commun., 1:373 (1989)) and HLA class 1 specific antigens (White et al., Anticancer Res., 10:1515 (1990)); activation of protein kinase C (Breton et al., Cancer Commun., 2:333 (1990)); stimulation (5-10 fold increase) of bone marrow (BM) proliferation (White et al., Cancer Commun., 3:83 (1991)); engraftment efficiency, and colony-forming unit activity (CFU-GM, CFU-GEMM, and BFU-E) as assessed by both in vivo and in vitro assays. Swainsonine has also been shown to confer protection against toxicity induced by high dose chemotherapy, to stimulate BM cell proliferation, and to accelerate recovery of BM cellularity when used in combination with chemical agents commonly used in treatment of human malignancies, (J. Nat. Cancer Inst., 83:1125, 1991). Published European Patent Application 0 104 826 also discloses swainsonine; moreover, it indicates therapeutic dosages and how they are determined for use in treating diseases accompanied by depressed immunoactivity.
Swainsonine offers a number of advantages over recombinant growth factors and cytokines. It is possible that swainsonine induces the simultaneous paracrine production, in modest quantities, of a number of cytokines. This effect may allow marrow protection in the absence of toxicity and the complexities involved in administration of one or more growth factors to an individual. In addition, swainsonine has biological activity when administered orally. Therefore, the potential exists for a convenient route of administration of swainsonine which is not possible using recombinant proteins. Furthermore, the simplicity of the molecule may facilitate inexpensive production of a suitable formulation.
With regard to the synthesis of (-)-swainsonine, several enantioselective syntheses of the natural alkaloid have been reported. Many of these utilize carbohydrates as chiral precursors. Syntheses from D-mannose [Gonzales et. al., Bull. Chem. Soc. Jpn., 65: 567 (1992); T. Takaya et al., Chem. Lett., 1201 (1984); G. W. J. Fleet et al., Tet. Lett., 25: 1853 (1984); G. W. J. Fleet et al., Tetrahedron, 43: 3083 (1987); G. W. J. Fleet et al., Tet. Lett. 30: 7261 (1989)], D-glucose [A. C. Richardson et al., Carb. Res. 136: 225 (1985); A. C. Richardson et al., J. Chem. Soc., Chem. Comm. 447 (1984); T. Saumi et al., Chem. Lett. 513 (1984); T. Saumi et al., Carb. Res., 136: 67 (1985))], D-erythrose [J. K. Cha et al., J. Amer. Chem. Soc., 111: 2580 (1989); W. H. Pearson, Tet. Lett., 52: 7571 (1990)], D-xlyxose [A. R. Chamberlain, J. Amer. Chem. Soc., 112: 8100 (1990)], D-ribonolactone [N. Iko

REFERENCES:
Chemical Abstracts, vol. 106, No. 17, 27 Apr. 1987, abstract No. 138253y, S. Hashimoto et al., p. 673.
Chemistry Letters, No. 1, 1985, pp. 31-34, N. Yasuda et al., p. 33.
Tetrahedron, vol. 43, No. 13, 1987, pp. 3095-3108; G. N. Austin et al., pp. 3097, 3106.
Chemical Abstracts, vol. 104, No. 23, 9 Jun. 1986, abstract No. 07151, T. Takatani et al, pp. 743-744, abstract.
Tetrahedron Letters, vol. 31, No. 2, 1990, pp. 169-170; W. A. Anderson et al, p. 170.
Tetrahedron Letters, vol. 33, No. 34, 18 Aug. 1992, pp. 4917-4920; Y. Chen et al. compound 2.
Copy International Search Report prepared by the EPO as the ISA dated 02 Feb. 1993.

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