Synthesis of N-substituted oligomers

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

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530317, 544 98, 544358, C07K 104

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active

058772782

ABSTRACT:
A solid-phase method for the synthesis of N-substituted oligomers, such as poly (N-substituted glycines) (referred to herein as poly NSGs) is used to obtain oligomers, such as poly NSGs of potential therapeutic interest which poly NSGs can have a wide variety of side-chain substituents. Each N-substituted glycine monomer is assembled from two "sub-monomers" directly on the solid support. Each cycle of monomer addition consists of two steps: (1) acylation of a secondary amine bound to the support with an acylating agent comprising a leaving group capable of nucleophilic displacement by --NH.sub.2, such as a haloacetic acid, and (2) introduction of the side-chain by nucleophilic displacement of the leaving group, such as halogen (as a solid support-bound .alpha.-haloacetamide) with a sufficient amount of a second sub-monomer comprising an --NH.sub.2 group, such as a primary amine, alkoxyamine, semicarbazide, acyl hydrazide, carbazate or the like. Repetition of the two step cycle of acylation and displacement gives the desired oligomers. The efficient synthesis of a wide variety of oligomeric NSGs using automated synthesis technology of the present method makes these oligomers attractive candidates for the generation and rapid screening of diverse peptidomimetic libraries. The oligomers of the invention, such as N-substituted glycines (i.e. poly NSGs) disclosed here provide a new class of peptide-like compounds not found in nature, but which are synthetically accessible and have been shown to possess significant biological activity and proteolytic stability.
Combinatorial libraries of cyclic compounds are disclosed wherein the cyclic compounds are comprised of at least one ring structure derived from cyclization of a peptoid backbone. The diversity of product compounds is generated by the sequential addition of substituted submonomers. The combinatorial library includes 10 or more, preferably 100 or more, and more preferably 1,000 or more distinct and different compounds. The library includes each of the product compounds in retrievable and analyzable amounts and preferably includes at least one biologically active compound. Methods of synthesizing the combinatorial libraries and assay devices produced using the libraries are disclosed as is methodology for screening for and obtaining biologically active cyclic organic compounds.

REFERENCES:
patent: 3634364 (1972-01-01), Greenbelt et al.
patent: 5143854 (1992-09-01), Pirrung et al.
patent: 5182366 (1993-01-01), Huebner et al.
patent: 5194392 (1993-03-01), Geysen
patent: 5225533 (1993-07-01), Rutter et al.
patent: 5252296 (1993-10-01), Zuckermann et al.
patent: 5266684 (1993-11-01), Rutter et al.
patent: 5288514 (1994-02-01), Ellman
patent: 5539083 (1996-07-01), Cook et al.
Zuckerman, Ronald et al., "Efficient Method for the Preparation of Peptoids Am. Chem. Soc. (1992) vol. 114:10646-10647.
Simon, Reyna et al., "Peptoids: A Modular Approach to Drug Discovery" Proc. Nat.l Acad. Sci. USA (1992) vol. 89:9367-9371.
Zuckerman, Ronald et al., "Efficient Method for the Preparation of Peptoids Chemtracts-Macromolecular Chemistry (1993) vol. 4:80-83.
Marcincin, Anton et al., "Studium Adheznych Vlastnosti N-Substituovanych Polyamidov.ll. Adhezna Praca N-Alkoxymetyl-Poly-Kaprolaktamu Kniektorym Polymerom", Plasty Kauc (1975) vol. 12:101-104.
Kasica, H. et al., "Electrical Conductivity of N-Substituted Polyamides", Journal of Polymer Science Part A-1 vol. 6:1615-1623.
Cosani A. et al., "N-Substituted Poly ( -amino acids). l. Synthesis and Characterization of Poly (N-methyl-y-mehtyl L-Glutamate) and Poly ( N-methyl-Y-ethyl L-glutamate).sup.1 ", Macromolecules (1978) vol. 11 No. 5;1041-1045.
Barrow, C.J. et al., "WIN 64821, A New Competitive Antagonist to Substance P, Isolated from an Aspergillus Species: Structure Determination and Solution Conformation", J.Org.Chem. (Apr. 1993) vol. 58:6016-6021.
Beebe, Xenia et al., "Polymer-Supported Synthesis of 2,5 Disubstituted Tetrahydrofurans" J.Am.Chem.Soc. (Jul. 1992) vol. 114:10061-10062.
Bunin, Barry A. and Ellman Jonathan A., "A General and Expedient Method for the Solid-Phase Synthesis of 1,4-Benzodiazephine Derivatives", J.Am.Chem.Soc. (Oct. 1992) vol. 114:10997-10998.
Bunin, Barry A. et al., "The Combinatorial Synthesis and Chemical and Biological Evaluation of a 1,4-Benzodiazephine Library", Proc.Natl.Acad.Sci. USA (May. 1994) vol. 91:4708-4712.
Chen, Chixu, et al., "`Analogous` Organic Synthesis of Small-Compound Libraries: Validation of Combinatorial Chemistry in Small-Molecule Synthesis," J. Am. Chem. Soc., (1994) vol. 116, pp. 2661-2662.
Cho, Charles Y., "An Unnatural Biopolymer," Science, (Sep. 3, 1993) vol. 261, pp. 1303-1305.
Chu, Min et al., "Two Novel Diketopiperazine Isolated From the Fungus Tolypocladium sp.", Tetrahedron Lett. (Sep. 1993) vol. 34, No. 47:7537-7540.
Deshpande, Milind S., "Formation of Carbon-Carbon Bond on Solid Support: Application of the Stille Reaction", Tetrahedron Lett. (1994) vol. 35, No. 31:5613-5614.
Furka, A., et al., "Cornucopia of Peptides by Synthesis", Dept. Org. Chem,
Gelin, Jacques et al., "Synthetic Studies on Thaxtomins A and B, Phytotoxins Associated with Streptomyces scabies, the Causal Organism of Potato Common Scab", J.Org.Chem. (Jun. 1993) vol. 58, No. 13:3473-3475.
Gordon, D.W. and Steele, J., "Reductive Alkylation on a Solid Phase: Synthesis of a Piperazinedione Combinatorial Library", Bioorg. and Med. Chem. Lett. (1995) vol. 5:47-50.
Hobbs-DeWitt, Sheila, et al., "`Diversomers`: An Approach to Nonpeptide, Nonoligomeric Chemical Diversity", Proc.Natl.Acad.Sci. USA (Aug. 1993) vol. 90:6909-6913.
Kanemasa, S. and Tsage, O., "N-Metalated Azomethine Ylides" Adv. Cycloaddition (1993) vol. 3:99-159.
Kates S.A. et al., "Automated Allyl Cleavage for Continuous-Flow Synthesis of Cyclic and Branched Peptides" Anal.Biochem. (1993) vol. 212:303-310.
Robey, F.A. et al. "Synthesis, Analyses and Uses of Site-Specific Bromoacetyl-Derivatized Synthetic Peptides: Starting Materials for Countless New Cyclic Peptides, Peptomers and Peptide Conjugates", Chimica Oggi (1992) 27-31.
Shimazaki, N. et al., "N.sup.6 -2,2 Diphenylethyl)adenosine, a Novel Adenosine Receptor Agonist with Antipsychotic-like Activity" (1987) vol. 30:1709-1711.
Stewart, J.M. and Young, J.D., "Solid Phase Peptide Synthesis", (2nd ed.), Pierce, Rockford, Il (1984) 30-31.
Yu, K.-L et al. "Heck Reactions in Solid Phase Synthesis", Tet.Lett. (Aug. 1994) vol. 35:8919-8922.
Zuckermann et al., "Discovery of Nanomolar Ligands for 7-Transmembrane G-Protein-Coupled Receptors from a Diverse N-(Substituted)glycine Peptoid Library" J.Med.Chem. (1994) vol. 37:2678-2685.

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