US2005171028A1PendingUtilityA1

Thioketals and thioethers for inhibiting the expression of VCAM-1

Individually held — no corporate assignee on recordPriority: Mar 21, 2000Filed: Feb 8, 2005Published: Aug 4, 2005
Est. expiryMar 21, 2020(expired)· nominal 20-yr term from priority
C07C 323/67C07C 323/20C07C 323/25C07C 323/60C07C 323/21C07H 15/203A61K 31/222A61K 31/225C07C 323/66C07C 323/56
48
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Claims

Abstract

Thioketals and thioethers are provided that inhibit the expression of VCAM-1, and which can be used in the treatment of VCAM-1 mediated diseases including inflammatory disorders, cardiovascular diseases, occular diseases, autoimmune diseases, neurological disorders, and cancer. The compounds also can be used to treat hyperlipidemia and/or hypercholesterolemia.

Claims

exact text as granted — not AI-modified
1 ) A compound of formula (I), or a pharmaceutically acceptable salt thereof:  
       
         
           
           
               
               
           
         
         wherein  
         a) R a , R b , R c , and R d  are independently any group that does not adversely affect the desired properties of the molecule, including hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkaryl, substituted alkaryl, aralkyl, or substituted aralkyl; and  
         b) Z is (i) a substituted or unsubstituted carbohydrate, (ii) a substituted or unsubstituted alditol, (iii) C 1-10 alkyl or substituted C 1-10 alkyl terminated by sulfonic acid, (iv) C 1-10 alkyl or substituted C 1-10 alkyl, terminated by phosphonic acid, (v) substituted or unsubstituted C 1-10 alkyl-O—C(O)—C 1-10 alkyl, (vi) straight chained polyhydroxylated C 3-10 alkyl; (vii) —(CR 2 ) 1-6 —COOH, wherein R is independently hydrogen, halo, amino, or hydroxy, and wherein at least one of the R substituents is not hydrogen; or (viii) —(CR 2 ) 1-6 —X, wherein X is aryl, heteroaryl, or heterocycle, and R is independently hydrogen, halo, amino, or hydroxy.  
       
     
     
         2 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl.  
     
     
         3 ) The compound of  claim 1  wherein Z is a substituted or unsubstituted monosaccharide, disaccharide, oligosaccharide, or polysaccharide.  
     
     
         4 ) The compound of  claim 1  wherein Z is substituted or unsubstituted furanose or pyranose.  
     
     
         5 ) The compound of  claim 1  wherein Z is threose, ribulose, ketose, gentiobiose, aldose, aldotetrose, aldopentose, aldohexose, ketohexose, ketotetrose, ketopentose, erythrose, threose, ribose, deoxyribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, glactose, talose, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, tagatose, dextrose, maltose, lactose, sucrose, cellulose, aldose, amylose, palatinose, trehalose, turanose, cellobiose, amylopectin, glucosamine, mannosamine, fucose, phamnose, glucuronate, gluconate, gluconolactone, muramic acid, abequose, rhamnose, gluconic acid, glucuronic acid, or galactosamine.  
     
     
         6 ) The compound of  claim 1  wherein Z is —CH 2 —(CHOH) 3 CH 2 OH.  
     
     
         7 ) The compound of  claim 1  wherein Z is —CH 2 —(CHOH) 4 CH 2 OH.  
     
     
         8 ) The compound of  claim 1  wherein Z is —(CR 2 ) 1-6 -sulfonic acid, and R is independently hydrogen, halo, amino, or hydroxy.  
     
     
         9 ) The compound of  claim 1  wherein Z is substituted or unsubstituted alditol.  
     
     
         10 ) The compound of  claim 1  wherein Z is —(CR 2 ) 1-6 -phosphonic acid, and R is independently hydrogen, halo, amino, or hydroxy.  
     
     
         11 ) The compound of  claim 1  wherein Z is —(CR 2 ) 1-4 -phosphonic acid, and R is independently hydrogen, halo, or hydroxy.  
     
     
         12 ) The compound of  claim 1  wherein Z is —(CHR) 1-6 —O—C(O)—(CHR) 1-6 —CH 2 R, and R is independently hydrogen, halo, amino, or hydroxy.  
     
     
         13 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is —(CR 2 ) 1-6 —X, wherein X is aryl, heteroaryl, or heterocycle, and R is independently hydrogen, halo, amino, or hydroxy.  
     
     
         14 ) The compound of  claim 1  wherein Z is —CH 2 —(CHR′) 1-8 —CH 2 R′, R′ is independently hydrogen or hydroxy, and at least two of R′ are hydroxy.  
     
     
         15 ) The compound of  claim 1  wherein Z is —CH 2 —(CHR′) 1-6 —CH 2 R′, R′ is independently hydrogen or hydroxy, and at least three of R′ are hydroxy.  
     
     
         16 ) The compound of  claim 1  wherein Z is —(CH 2 ) 0-6 —CF 2 —COOH.  
     
     
         17 ) The compound of  claim 1  wherein Z is —(CH 2 ) 1-6 —CH(NR 1 R 2 )—COOH, and R 1  and R 2  are independently hydrogen or lower alkyl.  
     
     
         18 ) The compound of  claim 1  wherein Z is —(CR 2 ) 1-6 —X, R is independently hydrogen, halo, amino, or hydroxy; and X is substituted or unsubstituted pyrolidine, imidazole, pyridine, or pyrimidine.  
     
     
         19 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-amino-3-carboxypropyl; 3-amino-4-carboxybutyl; 1,1-difluoro-1-carboxymethyl; phosphonomethyl; 1,1-difluoro-1-phosphono-methyl; 2-(2-carboxy-N-pyrrolidine)ethyl; (2H-imidazol-5-yl)methyl; 2-pyridylmethyl; 3-pyridylmethyl; or 5-pyrimidinylmethyl.  
     
     
         20 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is arabitol.  
     
     
         21 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is ribofuranose.  
     
     
         22 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-hydroxy-3-propyl-D-gluconate.  
     
     
         23 ) The compound of  claim 1  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-hydroxypropan-3-sulfonic acid.  
     
     
         24 ) A compound of formula (II) or its pharmaceutically acceptable salt:  
       
         
           
           
               
               
           
         
         wherein:  
         a) X is O, S, SO, SO 2 , CH 2 , or NH;  
         b) spacer is —(CH 2 ) n —, —(CH 2 ) n —CO—, —(CH 2 ) n —NH—, —(CH 2 ) n —O—, —(CH 2 ) n —S—, —(OCH 2 )—, —(SCH 2 )—, —(CH 2 S—), -(aryl-O)—, —(O-aryl)-, -(alkyl-O)—, —(O-alkyl)-; —O—C(O)—(CH 2 ) n , —(CH 2 ) n —C(O)—O—, S—C(S)—(CH 2 ) n , —(CH 2 ) n —C(S)—S—, —C(O)—, —C(S)—;  
         c) n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;  
         d) R 1  and R 2  are independently alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkaryl, or aralkyl;  
         e) R 3  and R 4  are independently any group that does not otherwise adversely affect the desired properties of the molecule, including H, halogen, or R 1 ; and  
         f) Y is aryl or heteroaryl monosubstituted by —C(O)NR 5 R 6 , wherein R 5  and R 6  are independently hydrogen or alkyl.  
       
     
     
         25 ) The compound of  claim 24  wherein: 
 a) —X-spacer- is —S—CH 2 —;    b) R 1  and R 2  are t-butyl;    c) R 3  and R 4  are hydrogen; and    d) Y is aryl or heteroaryl monosubstituted by —C(O)NR 5 R 6 , wherein R 5  and R 6  are independently hydrogen or alkyl.    
     
     
         26 ) The compound of  claim 24  which is 2,6-Di-tert-butyl-[4′-(N,N-diethylaminocarbonyl)benzyl]thiophenol.  
     
     
         27 ) The compound of  claim 24  which is 2,6-Di-tert-butyl-[4′-(N,N-dimethylaminocarbonyl)benzyl]thiophenol.  
     
     
         28 ) A pharmaceutical composition comprising the compound of  claim 1  and a pharmaceutically acceptable carrier.  
     
     
         29 ) The pharmaceutical composition of  claim 28  wherein Z is substituted or unsubstituted furanose or pyranose.  
     
     
         30 ) The pharmaceutical composition of  claim 28  wherein Z is substituted or unsubstituted alditol.  
     
     
         31 ) The pharmaceutical composition of  claim 28  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-amino-3-carboxypropyl; 3-amino-4-carboxybutyl; 1,1-difluoro-1-carboxymethyl; phosphonomethyl; 1,1-difluoro-1-phosphono-methyl; 2-(2-carboxy-N-pyrrolidine)ethyl; (2H-imidazol-5-yl)methyl; 2-pyridylmethyl; 3-pyridylmethyl; and 5-pyrimidinylmethyl.  
     
     
         32 ) The pharmaceutical composition of  claim 28  wherein R a , R b , R c , and R d  are t-butyl, and Z is arabitol.  
     
     
         33 ) The pharmaceutical composition of  claim 28  wherein R a , R b , R c , and R d  are t-butyl, and Z is ribofuranose.  
     
     
         34 ) The pharmaceutical composition of  claim 28  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-hydroxy-3-propyl-D-gluconate.  
     
     
         35 ) The pharmaceutical composition of  claim 28  wherein R a , R b , R c , and R d  are t-butyl, and Z is 2-hydroxypropan-3-sulfonic acid.  
     
     
         36 ) A method for treating a disease or disorder mediated by VCAM-1 comprising administering to a patient a VCAM-1 inhibiting effective amount of a compound of  claim 1 .  
     
     
         37 ) The method of  claim 36  wherein Z is substituted or unsubstituted furanose or pyranose.  
     
     
         38 ) The method of  claim 36  wherein Z is substituted or unsubstituted alditol.  
     
     
         39 ) A method for treating a disease or disorder mediated by VCAM-1 comprising administering to a patient a VCAM-1 inhibiting effective amount of a compound of  claim 24 .  
     
     
         40 ) The method of  claim 36  wherein the VCAM-1 mediated disease is an inflammatory disorder.  
     
     
         41 ) The method of  claim 37  wherein the VCAM-1 mediated disease is an inflammatory disorder.  
     
     
         42 ) The method of  claim 38  wherein the VCAM-1 mediated disease is an inflammatory disorder.  
     
     
         43 ) The method of  claim 39  wherein the VCAM-1 mediated disease is an inflammatory disorder.  
     
     
         44 ) The method of  claim 36  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         45 ) The method of  claim 37  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         46 ) The method of  claim 38  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         47 ) The method of  claim 38  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         48 ) The method of  claim 36  wherein the VCAM-1 mediated disease is a cardiovascular disease.  
     
     
         49 ) The method of  claim 37  wherein the VCAM-1 mediated disease is a cardiovascular disease.  
     
     
         50 ) The method of  claim 38  wherein the VCAM-1 mediated disease is a cardiovascular disease.  
     
     
         51 ) The method of  claim 39  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         52 ) The method of  claim 36  wherein the VCAM-1 mediated disease is an occular disease, an autoimmune disease, a neurological disorder, or cancer.  
     
     
         53 ) The method of  claim 37  wherein the VCAM-1 mediated disease is an occular disease, an autoimmune disease, a neurological disorder, or cancer.  
     
     
         54 ) The method of  claim 38  wherein the VCAM-1 mediated disease is an occular disease, an autoimmune disease, a neurological disorder, or cancer.  
     
     
         55 ) The method of  claim 39  wherein the VCAM-1 mediated disease is an inflammatory disorder selected from rheumatoid arthritis, osteoarthritis, asthma, dermatitis, psoriasis, organ transplantation or allograft rejection, autoimmune diabetes, and multiple sclerosis.  
     
     
         56 ) The method of  claim 36  wherein the VCAM-1 mediated disease is a cardiovascular disease selected from atherosclerosis, post-angioplasty restenosis, coronary artery disease, angina, small artery disease, diabetes mellitus, diabetic nephropathy, and diabetic retinopathy.  
     
     
         57 ) The method of  claim 37  wherein the VCAM-1 mediated disease is a cardiovascular disease selected from atherosclerosis, post-angioplasty restenosis, coronary artery disease, angina, small artery disease, diabetes mellitus, diabetic nephropathy, and diabetic retinopathy.  
     
     
         58 ) The method of  claim 38  wherein the VCAM-1 mediated disease is a cardiovascular disease selected from atherosclerosis, post-angioplasty restenosis, coronary artery disease, angina, small artery disease, diabetes mellitus, diabetic nephropathy, and diabetic retinopathy.  
     
     
         59 ) The method of  claim 39  wherein the VCAM-1 mediated disease is a cardiovascular disease selected from atherosclerosis, post-angioplasty restenosis, coronary artery disease, angina, small artery disease, diabetes mellitus, diabetic nephropathy, and diabetic retinopathy.  
     
     
         60 ) A method for treating hypercholesterolemia or hyperlipidemia comprising administering to a patient an effective treatment amount of a compound of  claim 1 .  
     
     
         61 ) The method of  claim 60  wherein Z is furanose or pyranose.  
     
     
         62 ) The method of  claim 60  wherein Z is substituted or unsubstituted alditol.  
     
     
         63 ) A method for treating hypercholesterolemia or hyperlipidemia comprising administering to a patient an effective treatment amount of a compound of  claim 24 .  
     
     
         64 ) The method of  claim 56  further comprising administering a platelet aggregation inhibitor, and antithrombotic agent, a calcium channel blocker, an angiotensin converting enzyme (ACE) inhibitor, or a β-blocker.  
     
     
         65 ) The method of  claim 57  further comprising administering a platelet aggregation inhibitor, and antithrombotic agent, a calcium channel blocker, an angiotensin converting enzyme (ACE) inhibitor, or a β-blocker.  
     
     
         66 ) The method of  claim 58  further comprising administering a platelet aggregation inhibitor, and antithrombotic agent, a calcium channel blocker, an angiotensin converting enzyme (ACE) inhibitor, or a β-blocker.  
     
     
         67 ) The method of  claim 59  further comprising administering a platelet aggregation inhibitor, and antithrombotic agent, a calcium channel blocker, an angiotensin converting enzyme (ACE) inhibitor, or a βblocker.  
     
     
         68 ) The method of  claim 40  further comprising administering a nonsteroidal antiinflammatory, a COX-2 inhibitor, a corticosteriod, or a TNF-α modulating agent.  
     
     
         69 ) The method of  claim 41  further comprising administering a nonsteroidal antiinflammatory, a COX-2 inhibitor, a corticosteriod, or a TNF-α modulating agent.  
     
     
         70 ) The method of  claim 42  further comprising administering a nonsteroidal antiinflammatory, a COX-2 inhibitor, a corticosteriod, or a TNF-α modulating agent.  
     
     
         71 ) The method of  claim 43  further comprising administering a nonsteroidal antiinflammatory, a COX-2 inhibitor, a corticosteriod, or a TNF-α modulating agent.

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