Automated allyl deprotection in solid-phase synthesis

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

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530333, 530334, 530337, 530340, C07K 106

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active

057770778

ABSTRACT:
A method for removing an allyl protecting group from an allyl-protected derivative of a biologically relevant amino acid is disclosed. One relevant aspect of the method is the use of soluble organometallic catalyst, such as an organopalladium catalyst. Preferably, soluble tetrakistriphenylphosphine palladium (0) is used. The allyl deprotection method now disclosed is suitable for use on an instrument for automated peptide synthesis. Methods of preparing the soluble organometallic catalyst are also disclosed, as are soluble catalyst compositions.

REFERENCES:
patent: 4314942 (1982-02-01), McCombie
patent: 4870199 (1989-09-01), Chen
patent: 4929671 (1990-05-01), Kunz et al.
patent: 5124448 (1992-06-01), Tschaen et al.
patent: 5214195 (1993-05-01), Kung et al.
patent: 5324786 (1994-06-01), Kunz et al.
Stevens and Watanabe, "Amino Acid Derivatives. I. Carboallyloxy Derivatives of .alpha.-Amino Acids," J. Am. Chem. Soc., 72:725-727 (Jan.-Apr. 1950).
Corey and Suggs, "Selective Cleavage of Allyl Ethers Under Mild Conditions by Transition Metal Reagents," J. Org. Chem. 38 (18) :3224 (1973).
Kunz and Dombo, "Solid Phase Synthesis of Peptides and Glycopeptides on Polymeric Supports with Allylic Anchor Groups," Angew. Chem. Int. Ed. Engl. , 27 (5) : 711-713 (1983).
Kunz and Waldmann, "The Allyl Group as Mildly and Selectively Removable Carboxy-Protecting Group for the Synthesis of Labile O-Glycopeptides," Angew. Chem. Int. Ed. Engl. , 23 (1) : 71-72 (1984).
Guibe, et al., "Palladium-Catalyzed Reaction of Tributyltin Hybrid. Selective and Very Mild Deprotection of Allyl and Allyloxycarbonyl Derivatives of Amino-Acids," Tetrahedron Letters, 27(21):2365-2368 (1986).
Dangles, et al., "Selective Cleavage of the Allyl and Allyloxycarbonyl Groups through Palladium-Catalyzed Hydrostannolysis with Tributyltin Hybride. Application to the Selective Protection-Deprotection of Amino Acid Derivatives and in Peptide Synthesis," J. Org. Chem., 52:4984-4993 (1987).
Deziel, "Mild Palladium (O) -Catalyzed Deprotection of Allyl Esters. A Useful Application in the Synthesis of Carbapenems and Other .beta.-Lactam Derivatives," Tetrahedron Letters, 28(38) :4371-4372 (1987).
Kunz, "Synthesis of Glycopeptides, Partial Structures of Biological Recognition Components," Angew. Chem. Int. Ed. Engl. , 26:294-308 (1987).
Kunz et al., "Allyl Ester as Temporary Protecting Group for the .beta.-Carboxy Function of Aspartic Acid," Int. J. Peptide Protein Res. 26:493-497 (1985).
Friedrich-Bochnitschek, et al., "Allyl Esters as Carboxy Protecting Groups in the Synthesis of O-Glycopeptides," J. Org. Chem., 54:751-756 (1989).
Baldwin, et al., "Asymmetric Amino Acid Synthesis: Preparation of the .beta.-Anion Derived from Aspartic Acid," J. Chem. Soc. Perkin Trans. , 833-834 (1989).
Baldwin, et al., "Non-Proteinogenic Amino Synthesis: Synthesis of .beta., .gamma.-Unsaturated .alpha.-Amino Acids from Aspartic Acid," Tetrahedron Letters, 45(19) :6319-6330 (1989).
Guibe et al., "Use of an Allylic Anchor Group and of its Palladium Catalyzed Hydrostannolytic Cleavage in the Solid Phase Synthesis of Protected Peptide Fragments," Tetrahedron Letters, 30: (20) :2641-2644 (1989).
Xaus, et al., "An Enzymatic Approach to the Synthesis of Convenient Aspartic Acid Intermediates in Peptide Chemistry, Synthesis of N-Benzyloxycarbonyl-L-Aspartic Acid .beta.-Allyl Esters," Tetrahedron Letters, 45(23) : 7421-7426 (1989).
Hayakawa, et al., "The Allylic Protection Method in Solid-Phase Oligonucleotide Synthesis. An Efficient Preparation of Solid-Anchored DNA Oligomers," J. Am. Chem. Soc., 112:1691-1696 (1990).
Belshaw, et al., "Chlorotrimethylsilane Mediated Formation of .omega.-Allyl Esters of Aspartic and Glutamic Acids," Synthetic Communications, 20(20) :3157-3160 (1990).
Kunz, "Allylic Anchoring Groups in the Solid Phase Synthesis of Peptides and Glycopeptides," Innovation and Perspectives in Solid Phase Synthesis (1990).
de la Torre, et. al., "Improved Method for the Synthesis of o-Glycosylated Fmoc Amino Acids to be used in Solid-Phase Glycopeptide Synthesis (Fmoc =fluoren -9-ylmethoxycarbonyl)," J. Chem. Soc., Chem. Commun., 965-867 (1990).
Barney, et al., "Novel Polyethylene Glycol-Polystyrene (PEG-PS) Graft Supports for Solid-Phase Peptide Synthesis," Peptides, pp. 267-268 (1992).
Kates, "A Novel, Convenient, Three-Dimensional Orthogonal Strategy for Solid-Phase Synthesis of Cyclic Peptides," Tetrahedron Letters, 34(10) :1549-1552 (Mar. 1993).
Barney, et al., "Biopolymer Syntheses on Novel Polyethylene Glycopolstyrene (PEG -PS) Graft Supports," pp. 603-604. (1992).
Zalipsky, et al., "Preparation and Use of an Aminoethyl Polyethylene Glycol-Crosslinked Polystyrene Graft Resin Support for Solid-Phase Peptide Synthesis," Solid Phase Methods, pp. 257-260. (1992).
Lawry & Richardson, Mechanism & Theory in Organic Chemistry, pp. 124-126, 138-139, 144-150 (1976).

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