US2011152209A1PendingUtilityA1

Core 2 GlcNAc-T Inhibitors

Assignee: BTG INT LTDPriority: Dec 22, 2003Filed: Feb 24, 2011Published: Jun 23, 2011
Est. expiryDec 22, 2023(expired)· nominal 20-yr term from priority
Inventors:Rakesh Chibber
A61P 43/00A61P 35/02A61P 9/10A61P 35/00A61P 9/00A61P 3/10A61P 35/04A61P 27/02A61P 29/00A61P 13/10A61P 15/00A61P 19/02A61P 11/06C07H 3/00A61P 1/16A61P 1/00A61P 13/08A61P 1/04A61K 31/702A61P 11/00A61P 1/02
40
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Claims

Abstract

The present invention relates to the use of known and novel compounds as inhibitors of UDP-GlcNAc:Galβ1,3GalNAc-R (GlcNAc to GalNAc) β1,6-N-acetylglucosaminyl transferase (core 2 β1,6 N-acetylaminotransferase, core 2 GlcNAc-T-EC 2.4.1.102). Such inhibitors have applications in therapy for diseases associated with raised activity of core 2 GlcNAc-T, in particular inflammatory diseases, atherosclerosis, diabetic cardiomyopathy, cancers—including treatment or prevention of metastasis—or diabetic retinopathy.

Claims

exact text as granted — not AI-modified
1 - 76 . (canceled) 
     
     
         77 . A method of treatment of a condition associated with raised activity of the enzyme core 2 GlcNAc-T comprising administration of an effective amount of a compound of the formula I to a patient in need thereof; 
       
         
           
           
               
               
           
         
         wherein R 1  is —OH, C 1-6  alkoxy, —NR 8 R 9 , or a monosaccharide of the formula IIa; 
       
       
         
           
           
               
               
           
         
         R 2  is —OH, C 1-6 alkoxy or a monosaccharide of the formula IIb: 
       
       
         
           
           
               
               
           
         
         R 3  is —OH, C 1-6 alkoxy or a monosaccharide of the formula IIc; 
       
       
         
           
           
               
               
           
         
         R 4  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; 
         R 5  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6  alkoxy-C 1-6 -alkyl; 
         R 6  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; 
         R 7  is C 2-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; 
         R 8  is H, C 1-6  alkyl or C 1-6  acyl; 
         R 9  is H, C 1-6  alkyl or C 1-6  acyl; and 
         Z is a steroid group; 
         or a pharmaceutically acceptable salt, ester or tautomeric form or derivative thereof. 
       
     
     
         78 . A method of treatment as described in  claim 77  in which R 1  is a monosaccharide of the formula IIa. 
     
     
         79 . A method of treatment as described in  claim 78  in which R 5  is C 1-6  alkyl or C 1-6  hydroxyalkyl. 
     
     
         80 . A method of treatment as described in  claim 78  in which R 5  is —CH 3 , —C 2 H 5 , —CH 2 OH or —C 2 H 4 OH. 
     
     
         81 . A method of treatment as described in  claim 77  in which R 3  is a monosaccharide of the formula IIc. 
     
     
         82 . A method of treatment as described in  claim 81  in which R 7  is C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl. 
     
     
         83 . A method of treatment as described in  claim 81  in which R 7  is —CH 2 OH or C 1-6  alkoxymethyl. 
     
     
         84 . A method of treatment as described in  claim 81  in which R 7  is —CH 2 OH. 
     
     
         85 . A method of treatment as described in  claim 77  in which the compound of the formula I is a compound of the formula III: 
       
         
           
           
               
               
           
         
         wherein: 
         R 4  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl, 
         R 5  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; and 
         R 7  is C 2-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl. 
       
     
     
         86 . A method of treatment as described in  claim 85  in which R 4  is C 1-6  alkyl, C 1-6  hydroxyalkyl. 
     
     
         87 . A method of treatment as described in  claim 85  in which R 4  is —CH 2 OH or —CH 3 . 
     
     
         88 . A method of treatment as described in  claim 85  in which R 5  is C 1-6  alkyl, C 1-6  hydroxyalkyl. 
     
     
         89 . A method of treatment as described in  claim 85  in which R 5  is —CH 3 , —C 2 H 5 , —CH 2 OH or —C 2 H 4 OH. 
     
     
         90 . A method of treatment as described in  claim 85  in which R 7  is C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl. 
     
     
         91 . A method of treatment as described in  claim 85  in which R 7  is —CH 2 OH or C 1-6 alkoxymethyl. 
     
     
         92 . A method of treatment as described in  claim 85  in which R 7  is —CH 2 OH. 
     
     
         93 . A method as described in  claim 85  wherein compounds of the formula III are compounds of the formula I wherein:
 R 1  is rhamnose; 
 R 2  is —OH; 
 R 3  is glucose; and 
 R4 is CH 2 OH. 
 
     
     
         94 . A method as described in  claim 85  wherein compounds of the formula III are compounds of the formula IV 
       
         
           
           
               
               
           
         
       
     
     
         95 . A method as described in  claim 77  in which the compound of the formula I is a compound of the formula V: 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  is OH, C 1-6  alkoxy or NR 8 R 9 , or a monosaccharide of the formula IIa: 
         R 4  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; 
         R 5  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6  alkyl; 
         R 6  is C 1-6  alkyl, C 1-6  hydroxyalkyl or C 1-6 -alkoxy-C 1-6 -alkyl; 
         R 8  is H, C 1-6  alkyl or C 1-6  acyl; 
         R 9  is H, C 1-6  alkyl or C 1-6  acyl; and 
         Z is a steroid group. 
       
     
     
         96 . A method as described in  claim 95  in which R 1  is OH, or NR 8 R 9 . 
     
     
         97 . A method as described in  claim 95  in which R 1  is NR 8 R 9 ;
 R 8  is H, C 1-6  alkyl or C 1-6  acyl; and 
 R 9  is H, C 1-6  alkyl or C 1-6  acyl. 
 
     
     
         98 . A method as described in  claim 95  in which R 1  is NR 8 R 9 ;
 R 8  is H; and 
 R 9  is H, C 1-6  alkyl or C 1-6  acyl. 
 
     
     
         99 . A method as described in  claim 95  in which R 1  is NR 8 R 9  
 R 8  is H; and 
 R 9  is C 1-6 acyl. 
 
     
     
         100 . A method as described in  claim 95  in which R 1  is NR 8 R 9 ;
 R 8  is H; and 
 R 9  is —COCH 3 . 
 
     
     
         101 . A method as described in  claim 95  in which the compound of formula IV is Galβ1->3(6-deoxy)GalNAcα-Z. 
     
     
         102 . A method according to  claim 77  in which the steroid group is a group of the formula VII: 
       
         
           
           
               
               
           
         
         wherein: 
         R 12  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 13  is H, —OH, ═O, or C 1-6  alkyl; 
         R 14  is H, —OH or C 1-6  alkyl or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
         R 15  is H, or —OH, or R 15  and R 33  taken together are ═O; 
         R 16  is H, —OH or ═O; 
         R 17  is H, —OH or ═O; 
         R 18  is H, —OH, C 1-6  alkoxy or C 1-6  alkyl; 
         R 19  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 20  is H, —OH, C 1-6  alkoxy or C 1-6  alkyl; 
         R 21  is H, —OH, C 1-6  alkyl, C 1-6  alkoxy or is a group of the formula VIII: 
       
       
         
           
           
               
               
           
         
         R 22  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 23  is H, —OH, C 1-6  alkyl, C 1-6  hydroxyalkyl, C 1-6 -alkoxy-C 1-6 -alkyl, ═CH 2  or ═CH—C 1-6 -alkyl; 
         R 24  is H, C 1-6  alkyl, C 1-6  acyl or a monosaccharide MS; 
         R 28  and R 29  are the same or different and are H or —OH; 
         R 32  is H, —OH or ═O; 
         R 33  is H, or R 33  and R 15  taken together are ═O, or R33 and R14 taken together represent the second bond of a double bond joining adjacent carbon atoms; MS is selected from a group consisting of rabinose, xylose, lyxose, ribose, glucose, mannose, galactose, allose, altrose, gulose, idose, talose, ribulose, xylulose, fructose, sorbose, tagatose, psicose, sedoheptulose, deoxyribose, fucose, rhamnose, 2-deoxy-glucose, quinovose, abequose, glucosamine, mannosamine, galactosamine, neurminic acid, muramic acid, N-acetyl-glucosannine, N-acetyl-mannosamine, N-acetyl-galactosmine, N-acetylneuraminic acid, N-acetylmuramic acid, O-acetylneuraminic acid, N-glycolylneuraminic acid, fructuronic acid, tagaturonic acid, glucuronic acid, mannuronic acid, galacturonic acid, iduronic acid, sialic acid and guluronic acid; and 
         Y is N or O. 
       
     
     
         103 . A method according to  claim 102  in which Y is O. 
     
     
         104 . A method according to  claim 102  in which R 21  is a group of the formula VIII. 
     
     
         105 . A method according to  claim 104  in which R 24  is C 1-6  alkyl, C 1-6  acyl or a monosaccharide MS. 
     
     
         106 . A method according to  claim 104  in which R 24  is C 1-6  acyl or a monosaccharide MS. 
     
     
         107 . A method according to  claim 104  in which R 24  is a monosaccharide MS. 
     
     
         108 . A method according to  claim 105 , in which MS is selected from the group consisting of glucose, galactose, mannose, fucose, N-acetyl-glucosamine, N-acetyl-galactosamine and sialic acid. 
     
     
         109 . A method according to  claim 105 , in which MS is glucose. 
     
     
         110 . A method according to  claim 104  in which R 23  is C 1-6  alkyl, C 1-6  hydroxyalkyl, C 1-6 -alkoxy-C 1-6 -alkyl, ═CH 2  or ═CH—C 1-6 -alkyl. 
     
     
         111 . A method according to  claim 104  in which R 23  is C 1-6  alkyl, C 1-6  hydroxyalkyl or ═CH 2 . 
     
     
         112 . A method according to  claim 104  in which R 23  is —C 2 H 4 OH, —CH 2 OH, C 1-6  alkyl, or ═CH 2 . 
     
     
         113 . A method according to  claim 104  in which R 23  is —C 2 H 4 OH, —CH 2 OH, —C 2 H 5 , —CH 3  or ═CH 2 . 
     
     
         114 . A method according to  claim 104  in which R 23  is —CH 3 . 
     
     
         115 . A method according to  claim 104  in which R 23  is ═CH 2 . 
     
     
         116 . A method of  claim 104  in which R 22  is H, —OH, or C 1-6  alkoxy. 
     
     
         117 . A method of  claim 104  in which R 22  is H. 
     
     
         118 . A method of  claim 102  in which R 19  is H, —OH, or C 1-6  alkyl. 
     
     
         119 . A method of  claim 102  in which:
 R 12  is H, —OH 
 R 13  is H or —OH; 
 R 14  is H, or —OH or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
 R 15  is H, or R 15  and R 33  taken together are ═O; 
 R 18  is H, —OH or C 1-6  alkoxy; 
 R 19  is C 1-6  alkyl; 
 R 20  is H, —OH or C 1-6  alkoxy; 
 R 32  is H, —OH or ═O; and 
 R 33  is H, or R 33  and R 15  taken together are ═O, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms. 
 
     
     
         120 . A method of  claim 102  in which:
 R 16  is H or ═O; 
 R 17  is H or —OH; 
 R 18  is H or —OH; and 
 R 20  is —OH or C 1-6  alkoxy. 
 
     
     
         121 . A method of  claim 102  in which the steroid group is selected from a group consisting of: 
       
         
           
           
               
               
           
         
         wherein: 
         R 18  is H or —OH; 
         R 20  is —OH or C 1-6  alkoxy; 
         R 24  is glucose or C 1-6  acyl; and 
         R 29  is H or —OH. 
       
     
     
         122 . A method of  claim 77  in which the compound of the formula I is selected from the group consisting of
 trigoneoside IVa which is (3β,25S)-26-(β3-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl-O-α-L-rhamnopyranosyl-(I->2)-O- 
 [β-D-glucopyranosyl-(1->4)]-β-D-glucopyranoside, glycoside F which is (3β)-26-(β-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl-O-α-L-rhanmopyranosyl-(1->2)-O-[β-D-glucopyranosyl-(1->4)]-β-D-glucopyranoside, shatavarin 1, compound 3, pardarinnoside C. 
 
     
     
         123 . A method according to  claim 77  in which the steroid group is a group of the formula VIII: 
       
         
           
           
               
               
           
         
         wherein: 
         R 12  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 13  is H, —OH, ═O, or C 1-6  alkyl; 
         R 14  is H, —OH or C 1-6  alkyl or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
         R 15  is H, or —OH, or R 15  and R 33  taken together are ═O; 
         R 16  is H, —OH or ═O; 
         R 17  is H, —OH or ═O; 
         R 18  is H, —OH, C 1-6  alkoxy or C 1-6  alkyl; 
         R 19  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 20  is H, —OH, C 1-6  alkoxy or C 1-6  alkyl; 
         R 27  is H, —OH, C 1-6  alkyl, C 1-6  alkoxy or C 1-6  hydroxyalkyl; 
         R 28  and R 29  are the same or different and are H or —OH; 
         R 32  is H, —OH or ═O; and 
         R 33  is H, or R 33  and R 15  taken together are ═O, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms. 
       
     
     
         124 . A method of  claim 123  in which R 27  is H, C 1-6  alkyl, or C 1-6  alkoxy. 
     
     
         125 . A method of  claim 123  in which R 27  is H, or C 1-6  alkyl. 
     
     
         126 . A method of  claim 123  in which R 19  is H, —OH, or C 1-6  alkyl. 
     
     
         127 . A method of  claim 123  in which R 20  is —OH or C 1-6  alkoxy. 
     
     
         128 . A method of  claim 123  in which
 R 12  is H or —OH 
 R 13  is H or —OH; 
 R 14  is H, or —OH or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
 R 15  is H, or R 15  and R 33  taken together are ═O; 
 R 16  is H, —OH or ═O; 
 R 17  is H, —OH or ═O; 
 R 18  is H, —OH or C 1-6 alkoxy 
 R 19  is C 1-6  alkyl; 
 R 32  is H, —OH or ═O; and 
 R 33  is H, or R 33  and R 15  taken together are ═O, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms. 
 
     
     
         129 . A method of  claim 123  in which the compound of the steroid group is a compound of the formula IXa 
       
         
           
           
               
               
           
         
       
     
     
         130 . A method of  claim 123  in which the compound of the formula I is a compound of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         131 . A method of  claim 77  in which the steroid group is of the formula XI: 
       
         
           
           
               
               
           
         
         wherein: 
         R 12  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 13  is H, —OH, ═O, or C 1-6  alkyl; 
         R 14  is H, —OH or C 1-6  alkyl or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
         R 15  is H, or —OH, or R 15  and R 33  taken together are ═O; 
         R 16  is H, —OH or ═O; 
         R 17  is H, —OH or ═O; 
         R 18  is H, —OH, C 1-6  alkoxy or C 1-6  alkyl; 
         R 19  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 25  is H, —OH, C 1-6  alkyl or C 1-6  alkoxy; 
         R 26  is H, —OH, C 1-6  alkyl, C 1-6  hydroxyalkyl, C 1-6 -alkoxy-C 1-6 -alkyl, ═CH 2  or ═CH—C 1-6 -alkyl; 
         R 28  and R 29  are the same or different and are H or —OH; 
         R 31  is H or —OH; 
         R 32  is H, —OH or ═O; 
         R 33  is H, or R 33  and R 15  taken together are ═O, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
         R 34  is H or —OH; and 
         X is O, S or NH. 
       
     
     
         132 . A method of  claim 131  in which X is O or NH; 
     
     
         133 . A method of  claim 131  in which X is O; 
     
     
         134 . A method of  claim 131  wherein R 26  is C 1-6  alkyl, C 1-6  hydroxyalkyl, C 1-6 -alkoxy-C 1-6 -alkyl, ═CH 2  or ═CH—C 1-6 -alkyl. 
     
     
         135 . A method of  claim 131  wherein R 26  is C 1-6  alkyl, C 1-6  hydroxyalkyl or ═CH 2 . 
     
     
         136 . A method of  claim 131  wherein R 26  is —C 2 H 4 OH, —CH 2 OH, C 1-6  alkyl, or ═CH 2 . 
     
     
         137 . A method of  claim 131  wherein R 26  is —C 2 H 4 OH, —CH 2 OH, —C 2 H 5 , —CH 3  or ═CH 2 . 
     
     
         138 . A method of  claim 131  wherein R 26  is —CH 3  or ═CH 2 . 
     
     
         139 . A method of  claim 131  wherein R 19  is H, —OH, C 1-6  alkyl. 
     
     
         140 . A method of  claim 131  wherein R 19  is C 1-6  alkyl. 
     
     
         141 . A method of  claim 131  wherein:
 R 12  is H, or —OH; 
 R 13  is H, or —OH; 
 R 14  is H or R 14  and R 33  taken together represent the second bond of a double bond joining adjacent carbon atoms; 
 R 15  is H, or R 15  and R 33  taken together are ═O; 
 R 18  is H or —OH; 
 R 25  is H or —OH; 
 R 28  and R 29  are H; 
 R 31  is H or —OH; 
 R 33  is H, or R 33  and R 15  taken together are ═O, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms; and 
 R 34  is H or —OH. 
 
     
     
         142 . A method of  claim 131  wherein:
 R 15  is H; 
 R 16  is H or —OH; 
 R 17  is H or —OH; 
 R 32  is H or —OH; and 
 R 33  is H, or R 33  and R 14  taken together represent the second bond of a double bond joining adjacent carbon atoms. 
 
     
     
         143 . A method of  claim 131  in which the steroid group of the formula XI is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         144 . A method of  claim 131  in which the steroid group of the formula XI is selected from the group consisting of diosgenin, yamogenin, tigogenin, neotigogenin, sarsasapogenin, smilagenin, hecogenin, solasodine or tomatidine. 
     
     
         145 . A method of  claim 77  in which the compounds of the formula I are selected from the group consisting of:
 Shatavarin IV which is sarsasapogenin 3-O-α-L-rhamnopyranosyl-(1->2)-O-[β-D-glucopyranosyl-(1->4)]-β-D-glucopyranoside, 
 Compound 12 which is solasodine 3-O-α-L-rhamnopyranosyl-(1->2)-O-[β-D-glucopyranosyl-(1->4)]-(3-D-glucopyranoside, 
 Deltonin which is (3β,25R)-spirost-5-en-3-yl-O-α-L-rhamnopyranosyl-(1->2)-O-[β-D-glucopyranosyl-(1->4)]-β-D-Glucopyranoside, and 
 Balanitin VI is (3β,25S)-spirost-5-en-3-yl-O-α-L-rhamnopyranosyl-(1->2)-O-[β-D-glucopyranosyl-(1->4)]-β-D-Glucopyranoside. 
 
     
     
         146 . The method of  claim 77  in which the condition is an inflammatory disease, asthma, rheumatoid arthritis, atherosclerosis, inflammatory bowel disease, diabetic cardiomyopathy, myocardial dysfunction, cancer, cancer metastasis or diabetic retinopathy. 
     
     
         147 . The method of  claim 77  in which the condition is leukaemia, oral cavity carcinomas, pulmonary cancers such as pulmonary adenocarcinoma, colorectal cancer, bladder carcinoma, liver tumours, stomach tumours colon tumours, prostate cancer, testicular tumour, mammary cancer, lung tumours oral cavity carcinomas and any cancers where core 2 GlcNAc-T expression is raised above normal levels for that tissue type. 
     
     
         148 . The use of a compound disclosed in the method of  claim 77  in the manufacture of a medicament for the treatment of a condition associated with raised activity of the enzyme core 2 GlcNAc-T. 
     
     
         149 . Use as described in  claim 148  in which the condition is an inflammatory disease, asthma, rheumatoid arthritis, atherosclerosis inflammatory bowel disease, diabetic cardiomyopathy, myocardial dysfunction, cancer, cancer metastasis or diabetic retinopathy. 
     
     
         150 . Use as described in  claim 145  in which the condition is leukaemia, oral cavity carcinomas, pulmonary cancers such as pulmonary adenocarcinoma, colorectal cancer, bladder carcinoma, liver tumours, stomach tumours colon tumours, prostate cancer, testicular tumour, mammary cancer, lung tumours oral cavity carcinomas and any cancers where core 2 GlcNAc-T expression is raised above normal levels for that tissue type. 
     
     
         151 . A pharmaceutical composition comprising a compound disclosed in the method of  claim 77 . 
     
     
         152 . A compound of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         153 . Use of the compound of the formula XII as described in  claim 152  in therapy.

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