IP Library Granted Patent US 10,308,975
Granted Patent B2
US 10,308,975 · App. 15/887,735 · Granted Jun 4, 2019

Substituted imidazo[1,2-a]pyrazines as luciferase substrates

Inventors: Anton Shakhmin (Grover Beach, CA); Thomas Kirkland (Atascadero, CA); Joel Walker (San Luis Obispo, CA); Thomas Machleidt (Madison, WI); Mary Hall (Waunakee, WI); Keith V. Wood (Mount Horeb, WI)
Assignee: Promega Corporation
C12Q1/66A61K49/0013C07D487/04C07D519/00G01N33/581H04N1/6041G01N2333/90241
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Quick Facts
Patent No.
US 10,308,975
App. No.
15/887,735
Granted
Jun 4, 2019
Kind
B2
Abstract

Described are substituted imidazo[1,2-a]pyrazine compounds, which are coelenterazine analogs, kits comprising the compounds, and methods of using the compounds for the detection of luminescence in luciferase-based assays. Also described are methods for making the compounds, such as a method using aminopyrazine acetophosphonates as synthesis intermediates.

Claims (74)

1. A compound of formula (I):

or a tautomer or pharmaceutically acceptable salt thereof,

wherein:

R 1 is phenyl; and

q is 1;

wherein said phenyl is substituted with 1, 2, 3, 4, or 5 functional groups independently selected from the group consisting of cyano, carbamate, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkoxy, heteroalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, heterocycloalkyl, cycloalkylalkyl, heteroarylalkyl, arylalkyl, hydroxy, hydroxyalkyl, alkoxy, allyloxy, aryloxy, benzyloxy, amino, aminoalkyl, sulfonylamino, sulfinylamino, sulfonyl, sulfinyl, —COOH, amide, carbamate, silyl, silyloxy, sulfanyl, and acyl;

provided that R 1 is not

wherein R c is OH, OC(O)C 1 -C 7 -alkyl, or OCH 2 OC(O)C 1 -C 7 -alkyl.

2. The compound of claim 1 , or a tautomer or pharmaceutically acceptable salt thereof, wherein said phenyl is substituted with 1 or 2 functional groups independently selected from the group consisting of cyano, carbamate, alkyl, haloalkyl, heteroalkyl, aryl, hydroxy, alkoxy, allyloxy, amino, aminoalkyl, sulfonylamino, —COOH, and alkylsulfanyl.

3. The compound of claim 1 , wherein the compound is selected from the group consisting of:

8-benzyl-2-(3-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-hydroxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

tert-butyl (3-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)phenyl) carbamate;

2-(3-aminobenzyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-(tert-butyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

2-([1,1′-biphenyl]-4-ylmethyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

tert-butyl (4-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)phenyl)carbamate;

2-(4-aminobenzyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

2-(4-(allyloxy)-3-methoxybenzyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-hydroxy-3-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

4-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)benzoic acid;

8-benzyl-2-(3,5-bis (trifluoromethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

3-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)benzoic acid;

2-(3-(aminomethyl)benzyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

N-(3-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)phenyl) methanesulfonamide;

8-benzyl-2-(4-methoxy-3-(methoxymethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-(dimethylamino)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-(methoxymethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-(hydroxymethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3,4-dimethoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-(methylthio)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-((dimethylamino)methyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-ethoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-(2-methoxyethoxy)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one; and

3-((8-benzyl-3-oxo-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-2-yl)methyl)benzonitrile;

or a tautomer or pharmaceutically acceptable salt thereof.

4. A kit comprising a compound of claim 1 , or a tautomer or pharmaceutically acceptable salt thereof.

5. The kit of claim 4 , wherein the kit further comprises a luciferase.

6. The kit of claim 4 , wherein the kit further comprises a buffer reagent.

7. A method for detecting luminescence in a sample, the method comprising:

contacting a sample with a compound of claim 1 , or a tautomer or pharmaceutically acceptable salt thereof;

contacting the sample with a coelenterazine-utilizing luciferase, if it is not present in the sample; and

detecting luminescence.

8. The method of claim 7 , wherein the sample contains live cells.

9. The method of claim 7 , wherein the sample contains a coelenterazine-utilizing luciferase.

10. A method for detecting luminescence in a transgenic animal comprising:

administering a compound of claim 1 , or a tautomer or pharmaceutically acceptable salt thereof to a transgenic animal; and

detecting luminescence;

wherein the transgenic animal expresses a coelenterazine-utilizing luciferase.

11. A compound of formula (I):

or a tautomer or pharmaceutically acceptable salt thereof,

wherein:

R 1 is phenyl; and

q is 1;

wherein said phenyl is substituted with 2, 3, 4, or 5 functional groups independently selected from the group consisting of halogen, cyano, carbamate, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkoxy, heteroalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl, heterocycloalkyl, cycloalkylalkyl, heteroarylalkyl, arylalkyl, hydroxy, hydroxyalkyl, alkoxy, allyloxy, aryloxy, benzyloxy, amino, aminoalkyl, sulfonylamino, sulfinylamino, sulfonyl, sulfinyl, —COOH, amide, carbamate, silyl, silyloxy, sulfanyl, and acyl.

12. The compound of claim 11 , or a tautomer or pharmaceutically acceptable salt thereof, wherein said phenyl is substituted with 2, 3, 4, or 5 functional groups independently selected from the group consisting of halogen, haloalkyl, heteroalkyl, hydroxy, alkoxy, and allyloxy.

13. The compound of claim 11 , wherein the compound is selected from the group consisting of:

8-benzyl-2-(2,4-difluorobenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-fluoro-3-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-fluoro-3-hydroxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3-fluoro-4-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-fluoro-2-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

2-(4-(allyloxy)-3-methoxybenzyl)-8-benzyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-hydroxy-3-methoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-((perfluorophenyl)methyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3,5-bis (trifluoromethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(4-methoxy-3-(methoxymethyl)benzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one;

8-benzyl-2-(3,4-dimethoxybenzyl)-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one; and

8-benzyl-6-phenyl-2-(2,4,6-trifluorobenzyl)imidazo[1,2-a]pyrazin-3(7H)-one,

or a tautomer or pharmaceutically acceptable salt thereof.

14. A kit comprising a compound of claim 11 , or a tautomer or pharmaceutically acceptable salt thereof.

15. The kit of claim 14 , wherein the kit further comprises a luciferase.

16. The kit of claim 14 , wherein the kit further comprises a buffer reagent.

Assignments (2)
SECURITY INTEREST Recorded Apr 3, 2019
From: PROMEGA CORPORATION; PROMEGA BIOSCIENCES, LLC; TERSO SOLUTIONS, INC.; ORION SEVEN, LLC; PROMEGA AVIATION LLC
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 048790/0259 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 28, 2018
From: SHAKHMIN, ANTON; KIRKLAND, THOMAS; WALKER, JOEL; MACHLEIDT, THOMAS; HALL, MARY; WOOD, KEITH V.
To: PROMEGA CORPORATION
Reel/Frame 047006/0001 →
Continuity (3)
Division 15431961 · Feb 14, 2017
Provisional Application 62295363 · Feb 15, 2016
Related Publication 20180223330A1 · Aug 9, 2018