US2020063110A1PendingUtilityA1

Thienopyrrole compounds and uses thereof

Assignee: PROMEGA CORPPriority: Jun 25, 2015Filed: Nov 5, 2019Published: Feb 27, 2020
Est. expiryJun 25, 2035(~8.9 yrs left)· nominal 20-yr term from priority
C12N 9/0069C07D 491/048C12Y 113/12007C07D 493/04G01N 33/542C07D 207/34C07D 495/04C12Q 1/66G01N 33/581C07D 209/42C07K 5/0222C07K 5/0819
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Claims

Abstract

Thienopyrrole compounds that may inhibit Oplophorus-derived luciferases are disclosed, as well as compositions and kits comprising the thienopyrrole compounds, and methods of using the thienopyrrole compounds.

Claims

exact text as granted — not AI-modified
1 . A compound of formula (I), or a salt thereof: 
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; and 
         R 3  and R 4  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring. 
       
     
     
         2 . The compound of  claim 1 , wherein n is 1. 
     
     
         3 . The compound of any of  claims 1 - 2 , wherein the dashed line represents the presence of a bond, and X is CH. 
     
     
         4 . The compound of any of  claims 1 - 3 , wherein A is a 5-membered heteroaryl ring. 
     
     
         5 . The compound of any of  claims 1 - 4 , wherein A is a thienyl ring or a furanyl ring. 
     
     
         6 . The compound of any of  claims 1 - 3 , wherein A is a phenyl ring. 
     
     
         7 . The compound of any of  claims 1 - 6 , wherein R 1  is selected from the group consisting of hydrogen, C 1 -C 8  alkyl, halo-C 1 -C 8 -alkyl, alkoxyalkoxyalkyl and arylalkyl. 
     
     
         8 . The compound of any of  claims 1 - 7 , wherein R 1  is selected from the group consisting of hydrogen, ethyl, n-hexyl, 2-(2-methoxyethoxy)ethyl and benzyl. 
     
     
         9 . The compound of any of  claims 1 - 8 , wherein R 1  is ethyl. 
     
     
         10 . The compound of any of  claims 1 - 9 , wherein R 2  is optionally substituted aryl. 
     
     
         11 . The compound of  claim 10 , wherein R 2  is substituted phenyl. 
     
     
         12 . The compound of  claim 11 , wherein R 2  is phenyl substituted with one substituent selected from the group consisting of C 1 -C 4  alkyl, cyano, amido, C 1 -C 4  alkoxy, and hydroxyalkyl. 
     
     
         13 . The compound of  claim 12 , wherein R 2  is phenyl substituted with one methyl group. 
     
     
         14 . The compound of any of  claims 1 - 13 , wherein R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring. 
     
     
         15 . The compound of  claim 14 , wherein R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted monocyclic heterocycle. 
     
     
         16 . The compound of  claim 15 , wherein the optionally substituted monocyclic heterocycle is selected from the group consisting of optionally substituted pyrrolidine, piperidine and piperazine. 
     
     
         17 . The compound of  claim 15 , wherein the optionally substituted monocyclic heterocycle is selected from the group consisting of unsubstituted pyrrolidine, unsubstituted piperidine, piperidine substituted with one substituent, or piperazine substituted with one substituent. 
     
     
         18 . The compound of any of  claims 1 - 17 , wherein R 3  is hydrogen. 
     
     
         19 . The compound of any of  claims 1 - 18 , wherein R 4  is selected from the group consisting of unsubstituted C 1 -C 8  alkyl, halo-C 1 -C 8 -alkyl, carboxy-C 1 -C 8 -alkyl, C 1 -C 4 -alkoxycarbonyl-C 1 -C 8 -alkyl, optionally substituted phenyl, optionally substituted C 5 -C 6  cycloalkyl, optionally substituted C 5 -C 6 -cycloalkylalkyl, optionally substituted heterocyclyl, optionally substituted heteroarylalkyl, and optionally substituted heterocyclylalkyl. 
     
     
         20 . The compound of  claim 19 , wherein R 4  is phenyl that is unsubstituted or substituted with one substituent. 
     
     
         21 . The compound of  claim 20 , wherein the substituent is selected from the group consisting of C 1 -C 4 -alkoxycarbonyl and C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl. 
     
     
         22 . The compound of any of  claims 1 - 18 , wherein R 4  is cyclohexyl substituted with one substituent selected from the group consisting of carboxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 8 -alkylamido, hydroxy-C 1 -C 8 -alkylamido, amido, optionally substituted amino-C 1 -C 8 -alkylamido, C 1 -C 4 -dialkylamino-C 1 -C 8 -alkylamido, carboxy-C 1 -C 8 -alkylamido, sulfonic acid-C 1 -C 8 -alkylamido, sulfonate-C 1 -C 8 -alkylamido, C 1 -C 4 -alkylcarbonyl-C 1 -C 8 -alkylamido, optionally substituted C 3 -C 6 -cycloalkylamido, and optionally substituted heterocyclylamido. 
     
     
         23 . The compound of  claim 1 , wherein the compound has formula (Ia): 
       
         
           
           
               
               
           
         
       
     
     
         24 . The compound of  claim 1 , wherein the compound has formula (Ib): 
       
         
           
           
               
               
           
         
         wherein: 
         Y is selected from the group consisting of —NR a R b  and —OR c ; 
         R a  and R b  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, and optionally substituted heterocyclyl; or R a  and R b , together with the nitrogen atom to which they are attached, together form an optionally substituted ring; and 
         R c  is selected from the group consisting of hydrogen and optionally substituted C 1 -C 4  alkyl. 
       
     
     
         25 . The compound of  claim 24 , wherein Y is —OR c . 
     
     
         26 . The compound of  claim 25 , wherein R c  is selected from the group consisting of hydrogen and methyl. 
     
     
         27 . The compound of  claim 24 , wherein Y is —NR a R b . 
     
     
         28 . The compound of  claim 27 , wherein R a  and R b , together with the nitrogen atom to which they are attached, together form an optionally substituted ring. 
     
     
         29 . The compound of  claim 28 , wherein R a  and R b , together with the nitrogen atom to which they are attached, together form an optionally substituted monocyclic heterocycle. 
     
     
         30 . The compound of  claim 29 , wherein the optionally substituted monocyclic heterocycle is optionally substituted piperidine. 
     
     
         31 . The compound of  claim 30 , wherein the optionally substituted monocyclic heterocycle is selected from the group consisting of unsubstituted piperidine and piperidine substituted with one substituent. 
     
     
         32 . The compound of  claim 27 , wherein R a  is hydrogen. 
     
     
         33 . The compound of  claim 32 , wherein R b  is selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, and optionally substituted heterocyclyl. 
     
     
         34 . The compound of  claim 32 , wherein R b  is selected from the group consisting of hydrogen, C 1 -C 6  alkyl, hydroxyalkyl, optionally substituted aminoalkyl, carboxyalkyl, sulfonic acid-alkyl, sulfonate-alkyl, alkylcarbonylalkyl, optionally substituted C 3 -C 6 -cycloalkyl, and optionally substituted six-membered heterocyclyl. 
     
     
         35 . The compound of any of  claims 24 - 34 , wherein the compound has the following formula (Ib′) 
       
         
           
           
               
               
           
         
       
     
     
         36 . The compound of  claim 1 , wherein the compound is selected from the group consisting of:
 N-cyclohexyl-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-ethyl-2-(5-(pyrrolidine-1-carbonyl)-4H-thieno[3,2-b]pyrrol-4-yl)-N-(m-tolyl)acetamide;   N-ethyl-2-(5-(piperidine-1-carbonyl)-4H-thieno[3,2-b]pyrrol-4-yl)-N-(m-tolyl)acetamide;   ethyl 1-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carbonyl)piperidine-4-carboxylate;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-phenyl-4H-thieno[3,2-b]pyrrole-5-carboxamide;   ethyl 2-(4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)phenyl)acetate;   methyl 3-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)benzoate;   methyl-cis-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   8-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)octanoic acid;   6-(4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)piperidin-1-yl)-6-oxohexanoic acid;   trans-methyl-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylic acid;   N-(trans-4-(butylcarbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(trans-4-((2-hydroxyethyl)carbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-(trans-4-((2-(dimethylamino)ethyl)carbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)butanoic acid;   N-(trans-4-carbamoylcyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(trans-4-(hexylcarbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   ethyl 1-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carbonyl)piperidine-4-carboxylate;   methyl 6-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexanoate;   6-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexanoic acid;   1-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carbonyl)piperidine-4-carboxylic acid;   8-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)octanoic acid;   N-(trans-4-(cyclohexylcarbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(trans-4-((1-methylpiperidin-4-yl)carbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   tert-butyl 4-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)piperidine-1-carboxylate;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(trans-4-(piperidin-4-ylcarbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-(trans-4-((1-acetylpiperidin-4-yl)carbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   tert-butyl (6-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexyl)carbamate;   N-(trans-4-((6-(3′,6′-dihydroxy-3-oxo-3H-spiro[isobenzofuran-1,9′-xanthene]-5(6)-carboxamido)hexyl)carbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-(trans-4-((6-aminohexyl)carbamoyl)cyclohexyl)-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide hydrochloride;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(trans-4-((6-hydroxyhexyl)carbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   methyl-trans-4-(trans-4-(4-(2-(ethcyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)cyclohexane-1-carboxylate;   trans-4-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)cyclohexane-1-carboxylic acid;   (11S,14S,17S)-17-acetamido-11,14-bis(carboxymethyl)-1-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexyl)-1,10,13,16-tetraoxo-2,9,12,15-tetraazanonadecan-19-oic acid;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-methyl-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-cyclopentyl-4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(pyridin-4-ylmethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-N-(3-morpholinopropyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-ethyl-2-(5-(4-methylpiperazine-1-carbonyl)-4H-thieno[3,2-b]pyrrol-4-yl)-N-(m-tolyl)acetamide;   methyl 4-(2-oxo-2-(m-tolylamino)ethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate;   N-cyclohexyl-4-(2-oxo-2-(m-tolylamino)ethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   N-cyclohexyl-4-(24(2-(2-methoxyethoxy)ethyl)(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   methyl-trans-4-(4-(2-((2-(2-methoxyethoxy)ethyl)(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl 4-(2-(hexyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate;   N-cyclohexyl-4-(2-(hexyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   methyl-trans-4-(4-(2-(hexyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl 4-(2-(benzyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate;   6-(cis-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexanoic acid;   methyl 6-(trans-4-((4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)methyl)cyclohexane-1-carboxamido)hexanoate;   6-(trans-4-((4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)methyl)cyclohexane-1-carboxamido)hexanoic acid;   sodium 6-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexane-1-sulfonate;   potassium 6-(trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexane-1-sulfonate;   trans-4-(4-(2-(hexyl(m-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylic acid;   methyl trans-4-(4-(2-(ethyl(phenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-((3-cyanophenyl)(ethyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-((3-carbamoylphenyl)(ethyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(3-methoxyphenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(o-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(6-methyl-3,4-dihydroquinolin-1(2H)-yl)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(p-tolyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(4-(hydroxymethyl)phenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(1-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-1H-indole-2-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(1-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-6-methoxy-1H-indole-2-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-4H-furo[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   4-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-N-(trans-4-((6-hydroxyhexyl)carbamoyl)cyclohexyl)-4H-thieno[3,2-b]pyrrole-5-carboxamide;   sodium 6-(trans-4-(4-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxamido)hexane-1-sulfonate;   methyl trans-4-(4-(2-(ethyl(3-isopropylphenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(3-(hydroxymethyl)phenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-((3-(bromomethyl)phenyl)(ethyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-((3-(dimethylamino)phenyl)(ethyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(4-(2-(ethyl(3-isobutylphenyl)amino)-2-oxoethyl)-4H-thieno[3,2-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate;   methyl trans-4-(1-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-1H-indole-2-carboxamido)cyclohexane-1-carboxylate;   1-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-N-(trans-4-((6-hydroxyhexyl)carbamoyl)cyclohexyl)-1H-indole-2-carboxamide;   sodium 6-(trans-4-(1-(2-(ethyl(3-ethylphenyl)amino)-2-oxoethyl)-1H-indole-2-carboxamido)cyclohexane-1-carboxamido)hexane-1-sulfonate;   methyl trans-4-(1-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-1H-pyrrole-2-carboxamido)cyclohexane-1-carboxylate; and   methyl trans-4-(6-(2-(ethyl(m-tolyl)amino)-2-oxoethyl)-6H-thieno[2,3-b]pyrrole-5-carboxamido)cyclohexane-1-carboxylate.   
     
     
         37 . A method of inhibiting an  Oplophorus -derived luciferase the method comprising contacting the  Oplophorus -derived luciferase with a compound of any of  claims 1 - 36 . 
     
     
         38 . The method of  claim 37 , wherein the  Oplophorus -derived luciferase comprises a polypeptide sequence of SEQ ID NO: 2. 
     
     
         39 . A method of inhibiting an  Oplophorus -derived luciferase, the method comprising contacting the  Oplophorus -derived luciferase with a compound of formula (II): 
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring. 
       
     
     
         40 . The method of  claim 39 , wherein the  Oplophorus -derived luciferase comprises a polypeptide sequence of SEQ ID NO: 2. 
     
     
         41 . A method for modulating luminescence of an  Oplophorus -derived luciferase in a sample, the method comprising,
 (a) contacting the sample with a coelenterazine substrate and the compound of any of  claims 1 - 36 ; and   (b) detecting luminescence in the sample,   wherein the compound of any of  claims 1 - 36  causes a decrease in the luminescence from the  Oplophorus -derived luciferase.   
     
     
         42 . A method to detect an interaction between a first protein and a second protein in a sample, the method comprising:
 (a) contacting a sample with a coelenterazine substrate and the compound of any one of  claims 1 - 36 , wherein the sample comprises:
 (xvii) a first polynucleotide encoding a first fusion protein, wherein the first fusion protein comprises a first fragment of an  Oplophorus -derived luciferase and a first protein; and 
 (xviii) a second polynucleotide encoding a second fusion protein, wherein the second fusion protein comprises a second fragment of the  Oplophorus -derived luciferase and a second protein; and 
   (b) detecting luminescence in the sample,   
       wherein the detection of luminescence indicates an interaction between the first protein and the second protein. 
     
     
         43 . The method of any of  claims 41 - 42 , comprising contacting the sample with the coelenterazine substrate prior to contacting the sample with the compound of any one of  claims 1 - 36 . 
     
     
         44 . The method of  claim 42 , wherein when the first protein and second protein interact, the first fragment of the  Oplophorus -derived luciferase and the second fragment of the  Oplophorus -derived luciferase reconstitute a full-length enzyme capable of stably binding the coelenterazine substrate. 
     
     
         45 . A method to detect an interaction between a first protein and a second protein in a sample, the method comprising:
 (a) contacting a sample with a coelenterazine substrate and the compound of any one of  claims 1 - 36 , wherein the sample comprises:
 (xix) a first polynucleotide encoding a first fusion protein, wherein the first fusion protein comprises an  Oplophorus -derived luciferase and a first protein, wherein the  Oplophorus -derived luciferase is a bioluminescent donor; and 
 (xx) a second polynucleotide encoding a second fusion protein, wherein the second fusion protein comprises a fluorescent acceptor molecule and a second protein; 
   (b) detecting bioluminescence resonance energy transfer (BRET) in the sample, indicating an interaction or close proximity of the bioluminescent donor and the fluorescence acceptor.   
     
     
         46 . The method of any one of  claims 41 - 45 , wherein the sample comprises a cell. 
     
     
         47 . The method of  claim 46 , wherein the cell comprises the  Oplophorus -derived luciferase. 
     
     
         48 . The method of  claim 46 , wherein the cell expresses the  Oplophorus -derived luciferase. 
     
     
         49 . The method of any one of  claims 41 - 48 , wherein the coelenterazine substrate is a coelenterazine, coelenterazine derivatives, coelenterazine analogs, pro-coelenterazine, or quinone-masked coelenterazine. 
     
     
         50 . A bioluminescence resonance energy transfer (BRET) system comprising: a first fusion protein including a first target protein and a bioluminescence donor molecule, wherein the bioluminescence donor molecule is an  Oplophorus -derived luciferase ; a second fusion protein including a second target protein and a fluorescent acceptor molecule; a coelenterazine substrate, and the compound of any one of  claims 1 - 36 . 
     
     
         51 . A kit comprising:
 (a) a compound of any one of  claims 1 - 36 ; and   (b) an  Oplophorus -derived luciferase.   
     
     
         52 . The kit of  claim 51 , wherein the  Oplophorus -derived luciferase comprises a polypeptide sequence of SEQ ID NO: 2. 
     
     
         53 . The kit of any of  claims 51 - 52 , further comprising a coelenterazine substrate. 
     
     
         54 . The kit of any of  claims 51 - 53 , further comprising instructions for carrying out a luminescent assay. 
     
     
         55 . A method for modulating luminescence of an  Oplophorus -derived luciferase in a sample, the method comprising:
 (a) contacting the sample with a coelenterazine substrate and a compound of formula (II):   
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring; and 
         (b) detecting luminescence in the sample, 
         wherein the compound of formula (II) causes a decrease in the luminescence from the  Oplophorus -derived luciferase. 
       
     
     
         56 . A method to detect an interaction between a first protein and a second protein in a sample, the method comprising:
 (a) contacting a sample with a coelenterazine substrate and a compound of formula (II):   
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring, 
         wherein the sample comprises:
 (xxi) a first polynucleotide encoding a first fusion protein, wherein the first fusion protein comprises a first fragment of an  Oplophorus -derived luciferase and a first protein; and 
 (xxii) a second polynucleotide encoding a second fusion protein, wherein the second fusion protein comprises a second fragment of the  Oplophorus -derived luciferase and a second protein; and 
 
         (b) detecting luminescence in the sample, 
       
       wherein the detection of luminescence indicates an interaction between the first protein and the second protein. 
     
     
         57 . The method of any of  claims 55 - 56 , comprising contacting the sample with the coelenterazine substrate prior to contacting the sample with the compound of formula (II). 
     
     
         58 . The method of  claim 57 , wherein when the first protein and second protein interact, the first fragment of the  Oplophorus -derived luciferase and the second fragment of the  Oplophorus -derived luciferase reconstitute a full-length enzyme capable of stably binding the coelenterazine substrate. 
     
     
         59 . A method to detect an interaction between a first protein and a second protein in a sample, the method comprising:
 (a) contacting a sample with a coelenterazine substrate and a compound of formula (II):   
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring, 
         wherein the sample comprises:
 (xxiii) a first polynucleotide encoding a first fusion protein, wherein the first fusion protein comprises an  Oplophorus -derived luciferase and a first protein, wherein the  Oplophorus -derived luciferase is a bioluminescent donor; and 
 (xxiv) a second polynucleotide encoding a second fusion protein, wherein the second fusion protein comprises a fluorescent acceptor molecule and a second protein; 
 
         (b) detecting bioluminescence resonance energy transfer (BRET) in the sample, indicating an interaction or close proximity of the bioluminescent donor and the fluorescence acceptor. 
       
     
     
         60 . The method of any one of  claims 55 - 59 , wherein the sample comprises a cell. 
     
     
         61 . The method of  claim 60 , wherein the cell comprises the  Oplophorus -derived luciferase. 
     
     
         62 . The method of  claim 60 , wherein the cell expresses the  Oplophorus -derived luciferase. 
     
     
         63 . The method of any one of  claims 55 - 62 , wherein the coelenterazine substrate is coelenterazine substrate is a coelenterazine, coelenterazine derivatives, coelenterazine analogs, pro-coelenterazine, or quinone-masked coelenterazine. 
     
     
         64 . A bioluminescence resonance energy transfer (BRET) system comprising: a first fusion protein including a first target protein and a bioluminescence donor molecule, wherein the bioluminescence donor molecule is an  Oplophorus -derived luciferase; a second fusion protein including a second target protein and a fluorescent acceptor molecule; a coelenterazine substrate; and a compound formula (II): 
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cy cl oal kyl al kyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring. 
       
     
     
         65 . A kit comprising:
 (a) a compound of formula (II):   
       
         
           
           
               
               
           
         
         wherein: 
         the dashed line represents the presence or absence of a bond; 
         n is 0, 1, 2, 3, 4 or 5; 
         X is CH, N, O, or S;
 wherein, when the dashed line represents the presence of a bond, X is CH or N, and when the dashed line represents the absence of a bond, X is O or S; 
 
         A is an optionally substituted phenyl ring, or an optionally substituted 5- or 6-membered heteroaryl ring; 
         R 1  and R 2  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, optionally substituted alkoxyalkyl and optionally substituted alkoxyalkoxyalkyl; 
         Z is selected from the group consisting of —NR 3 R 4  and —OR 5 ; and 
         R 3 , R 4  and R 5  are each independently selected from the group consisting of hydrogen, optionally substituted C 1 -C 8  alkyl, optionally substituted C 3 -C 8 -cycloalkyl, optionally substituted C 3 -C 8 -cycloalkylalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heterocyclyl, and optionally substituted heterocyclylalkyl; or R 3  and R 4 , together with the nitrogen atom to which they are attached, together form an optionally substituted ring; and 
         (b) an  Oplophorus -derived luciferase. 
       
     
     
         66 . The kit of  claim 65 , wherein the  Oplophorus -derived luciferase comprises a polypeptide sequence of SEQ ID NO: 2. 
     
     
         67 . The kit of any of  claims 65 - 66 , further comprising a coelenterazine substrate. 
     
     
         68 . The kit of any of  claims 65 - 67 , further comprising instructions for carrying out a luminescent assay.

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