Exendin analogues, processes for their preparation and...

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Peptide containing doai

Reexamination Certificate

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C514S866000, C530S324000

Reexamination Certificate

active

06767887

ABSTRACT:

This invention concerns new exendin analogues which can be used in the therapy of diabetes mellitus, processes for their production and pharmaceutical preparations containing them.
BACKGROUND OF THE INVENTION
A functional connection between the small intestine and exocrine pancreas was proven in the 1960's after it became possible to accurately determine insulin in plasma. The insulin response after oral glucose administration is much stronger than after intravenous glucose administration even if identical plasma levels of glucose are reached. This “incretin effect” is explained by the functional combination of the entero-insular axis. Intestinal hormones are responsible for this effect which are released from the small intestine after meals, circulate in the plasma at increased measurable levels and amplify glucose-induced insulin release. In addition to the classical incretin hormone gastric inhibitory polypeptide I (GIP), glucagon-like peptide. 1 (GLP-1) is nowadays of primary interest. In a relatively short time GLP-1 has matured from being the physiologically most interesting incretin hormone candidate to a potential alternative for the treatment of diabetes mellitus type II. The present invention describes new substances which imitate the effect of the naturally occurring GLP-1 molecule. These new substances are characterized by an increased stability while maintaining efficacy.
Anti-diabetogenic Action
Infusion and subcutaneous injection of GLP-1 cause a considerable increase of insulin secretion and an inhibition of glucagon release in patients with diabetes mellitus type II (Gutniak, M. (1992); Kreymann, B. (1987); Nathan, D. M. (1992); Nauck, M. A. (1993a & b)). Both are of therapeutic interest and are involved in the blood sugar lowering effect of GLP-1: insulin promotes glucose uptake by its target tissue and inhibits gluconeogenesis. Furthermore GLP-1 analogues would be expected to increase glucose uptake in the periphery. The inhibition of glucagon secretion must be regarded as an indirect GLP-1 effect since glucagon-producing A cells express no GLP-1 receptors (Komatsu, R. (1989)). On the contrary, the increased insulin and somatostatin release appear to be the decisive factor. Both hormones are known as inhibitors of glucagon release.
Two molecular mechanisms certainly contribute to the GLP-1-induced insulin release in diabetes mellitus type II. In addition to directly amplifying the glucose-induced insulin release, GLP-1 sensitizes a subgroup of B cells towards the key stimulus “glucose” (Fehmann, H. C. (1991)) and possibly also towards further stimuli so that overall more B cells secrete insulin. This prizing affect is the most likely explanation for the fact that GLP-1 leads to a prolonged release of insulin despite its relatively short plasma half-life.
This effect depends on increased glucose levels (>108 mg/dl) (Göke, R. (1993a)). It distinguishes GLP-1 fundamentally from the sulfonylureas which influence insulin secretion independently of the plasma level of glucose. If the glucose value decreases below 108 mg/dl, the insulin secretion dries up even with an intravenous infusion of GLP-1. Hence hypoglycaemias would be hardly expected when GLP-1 is used therapeutically. In fact they have also not been described in the previous clinical studies. However, the pharmacokinetic properties of GLP-1 are problematic. The duration of action is limited due to its very short half-life.
From a therapeutic point of view the synthesis of stable and strongly effective GLP-1 peptide analogues is in any case desirable. Peptide analogues have now been synthesized based on the molecule exendin that was originally isolated from the venom of lizards with the aim of developing improved therapeutic agents that are stable towards degradation with an increased duration of action for the treatment of diabetes mellitus. These peptides have the same pharmacological effect as GLP-1, but surprisingly have a considerably longer half-life.
The new peptide sequences described as the subject matter of the invention have an effect on insulin synthesis and insulin release and an action on the insulin effect especially the uptake of glucose into the target tissues, muscle and fat tissue as well as emptying of the stomach.
SUBJECT MATTER OF THE INVENTION
The present invention is based on the sequence of exendin-3 and exendin-4, peptides which were isolated from the secretory product of
Heloderma horridum
or
Heloderma suspectum
(Eng. J. et al. (1990, 1992)). The amino acid sequence and effect of the two peptides on the pancreas has already been published by several authors (Eng. J. et a. (1990); Raufman, J. P. (1992); Göke, R. (1993b); Thorens, B. (1993)). The subject matter of this invention are new truncated exendin fragments which comprise the amino acid sequences of exendin-3-(1-30) or exendin-4-(1-30) in which the C-terminal end of these sequences can be shortened by up to 3 amino acids, preferably by at most 1 amino acid, and the N-terminal end can be shortened by up to 2 and preferably at most 1 amino acid. Surprisingly these exendin fragments are biologically active although the amino acid sequence is shortened. Shortened amino acid sequences are more economical to produce than relatively longer sequences. Hence, peptide fragments with the following sequences are particularly preferred; especially peptide fragments that are based on exendin-3-(1-30) (SEQ ID NO.1):
SEQ ID NO:1 based on exendin-3
1       5         10        15
H S D G T F T S D L S K Q M E E E A V

20        25        30
R L F I E W L K N G X
1
SEQ ID NO:2 based on exendin-4
1       5         10        15
H G E G T F T S D L S K Q M E E E A V

20        25        30
R L F I E W L K N G X
1
in which the amino acids at position 1, 2, 28, 29 or 30 can be part of the sequence depending on the desired chain length. The peptides are numbered through from the N-terminus to the C-terminus. X
1
denotes a proteogenic or non-proteogenic amino acid apart from glycine. Exendin and exendin analogues with a chain length of 1-27 are preferred and especially those with a chain length of 1-30.
The carboxyl group COR
3
of the amino acid at the C-terminal end can be present in a free form (R
3
=OH) or in the form of a physiologically tolerated alkaline or alkaline earth salt such as e.g. a sodium, potassium or calcium salt. The carboxyl group can also be esterified with primary, secondary or tertiary alcohols such as e.g. methanol, branched or unbranched C
1
-C
6
-alkyl alcohols, in particular ethyl alcohol or tert. butanol. The carboxyl group can, however, also be amidated with primary or secondary amines such as ammonia, branched or unbranched C
1
-C
6
alkylamines or C
1
-C
6
di-alkylamines, in particular methylamine or dimethylamine.
The amino group of the amino acid NR
1
R
2
at the N-terminal end can be present in a free form (R
1
, R
2
=H) or in the form of a physiologically tolerated salt such as e.g. a chloride or acetate. The amino group can also be acetylated with acids so that R
1
=H and R
2
=acetyl, trifluoroacetyl, adamantyl or be present in a form protected by conventional amino protecting groups of peptide chemistry such as e.g. Fmoc, Z, Boc, Alloc or be N-alkylated in which R
1
and/or R
2
=C
1
-C
6
alkyl or C
2
-C
8
alkenyl or C
7
-C
9
aralkyl.
Alkyl residues are understood as straight-chained, branched or optionally ring-shaped alkyl residues, preferably methyl, ethyl, isopropyl and cyclohexyl.
All exendin fragments can be present as completely or partially protected derivatives.
A further subject matter of this invention are exendin fragments with the above-mentioned propert

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