IP Library Granted Patent US 9,533,996
Granted Patent B2
US 9,533,996 · App. 14/853,856 · Granted Jan 3, 2017

Therapeutic thiophene-, furan-, and pyridine-fused azolopyrimidin-5-(6h)-ones

Inventors: Bryan Branstetter (Carlsbad, CA); James Breitenbucher (Escondido, CA); Brian Dyck (San Diego, CA); Laurent Gomez (San Diego, CA); Andrew Richard Hudson (San Diego, CA); Tami Jo Marrone (Carlsbad, CA); Marco Peters (San Diego, CA); Troy Vickers (San Diego, CA); Michael Weinhouse (Escondido, CA)
Assignee: Dart Neuroscience (Cayman) Ltd.
C07D495/14C07D471/14C07D487/14C07D491/107C07D491/147C07D491/22C07D495/12C07D495/22C07D498/08C07D519/00
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Quick Facts
Patent No.
US 9,533,996
App. No.
14/853,856
Granted
Jan 3, 2017
Kind
B2
Abstract

Described herein are compounds of Formula I and Formula II, methods of their synthesis, compositions comprising the compounds, and use of the compounds and compositions in treating numerous diseases and disorders, including cognitive deficits associated with CNS diseases and disorders.

Claims (64)

1. A compound of Formula I:

or a pharmaceutically acceptable salt thereof, wherein

A is O (oxygen) or S (sulfur);

X is CH or N (nitrogen);

M=1 or 2;

each occurrence of R 1 and R 2 is independently selected from H, halo, aryl, heteroaryl, —(C 1 -C 6 alkyl) aryl, —(C 1 -C 6 alkyl) heteroaryl, heterocycle, —CN, C 1 -C 6 alkyl, C 1 -C 6 thioalkyl, C 1 -C 6 thiohaloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, —OH, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, —NO 2 , —SO 2 C 1 -C 6 alkyl, —SOC 1 -C 6 alkyl, —SO 2 NH(C 1 -C 6 alkyl), —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), —CON(C 1 -C 6 alkyl) 2 , —C(O)O(C 1 -C 6 alkyl), —C(O)O(C 1 -C 6 alkyl)aryl, —OC(O)(C 1 -C 6 alkyl), —OC(O)(C 1 -C 6 alkyl)aryl, —SO 2 NH 2 , —CONH 2 , —CO 2 H, —COH, —NH 2 , C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, —N 3 , cyanate, isocyanate, thiocyanate, isothiocyanate, —(C 2 -C 6 alkenyl)O(C 1 -C 6 alkyl), —(C 1 -C 6 alkyl)O(C 1 -C 6 alkyl), —(C 1 -C 6 alkyl)O(C 1 -C 6 alkyl)O(C 1 -C 6 alkyl), aryloxy, arylthio, —CO(C 1 -C 6 alkyl), —CO(aryl), —CO(heteroaryl), and —CO(heterocycle);

or R 1 and R 2 are on adjacent carbons and are taken together with the carbons to which they are attached to form an optionally substituted 5-6 member saturated or unsaturated monocylic ring system, optionally comprising one or more oxygen, sulfur, or nitrogen atoms;

R 3 and R 4 are independently selected from H, halo, —CN, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, —OH, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, aryl, heteroaryl, —(C 1 -C 6 alkyl) aryl, —(C 1 -C 6 alkyl) heteroaryl, heterocycle, —NO 2 , —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), —CON(C 1 -C 6 alkyl) 2 , and —(CR 10 R 11 ) 0-3 NR 12 R 13 ;

or R 3 and R 4 taken together with the carbons to which they are attached form a saturated or unsaturated monocylic ring system, having the following structure:

D is O (oxygen), S (sulfur), —SO—, —SO 2 —, or —N—R 9 —;

m and n are independently 0-4, with the proviso that the sum of m and n is 1-5 when D is O (oxygen), S (sulfur), —SO—, —SO 2 —, —N—R 9 —;

R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are independently selected from —H, —F, —C 1 -C 6 alkyl, —C 1 -C 6 haloalkyl, —OH, —C 1 -C 6 alkoxy, —C 1 -C 6 haloalkoxy, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CO 2 (C 1 -C 6 alkyl), —CONH(C 1 -C 6 alkyl), and —CON(C 1 -C 6 alkyl) 2 ; and

R 9 , R 12 , and R 13 are independently selected from —H, —C 1 -C 6 alkyl, aryl, heteroaryl, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), —CON(C 1 -C 6 alkyl) 2 , —CO(C 1 -C 6 alkyl), —CO(aryl), —CO(heteroaryl), and —CO(heterocycle); or R 12 and R 13 taken together with the nitrogen to which they are attached form an optionally substituted heterocycle.

2. The compound of claim 1 , wherein one or more of R 1 , R 2 , R 3 , and R 4 is halomethyl.

3. The compound of claim 1 , wherein R 1 is H, and R 2 is C 1 -C 6 alkoxy; or R 1 is F, Cl, or Br, and R 2 is —CF 3 or —CHF 2 .

4. The compound of claim 1 , wherein A is S (sulfur); and X is N (nitrogen).

5. The compound of claim 1 , wherein R 3 is C 1 -C 6 alkyl; and R 4 is H, or

R 3 is C 1 -C 6 alkyl; and R 4 is —(CR 10 R 11 ) 0-3 NR 12 R 13 .

6. A compound of Formula I:

or a pharmaceutically acceptable salt thereof, wherein

A is O (oxygen) or S (sulfur);

X is CH or N (nitrogen);

M=1 or 2;

each occurrence of R 1 and R 2 is independently selected from —H, halo, —CN, —C 1 -C 3 alkyl, —C 1 -C 3 haloalkyl, —OH, —C 1 -C 3 haloalkoxy, —NO 2 , —SO 2 C 1 -C 3 alkyl, —SO 2 N(C 1 -C 3 alkyl) 2 , —CONH(C 1 -C 3 alkyl), and —CON(C 1 -C 3 alkyl) 2 ;

or R 1 and R 2 are on adjacent carbons and taken together with the carbons to which they are attached form a 5-6 member monocylic ring system comprising one or more oxygen atoms, wherein the ring system is optionally substituted with one or more F;

R 3 and R 4 are independently selected from H, F, Cl, Br, —CN, —C 1 -C 3 alkyl, —C 1 -C 6 , —CF 3 , —CHF 2 , —OH, —C 1 -C 3 alkoxy, —OCF 3 , —NO 2 , —SO 2 C 1 -C 3 alkyl, —SO 2 N(C 1 -C 3 alkyl) 2 , —CONH(C 1 -C 3 alkyl), —CON(C 1 -C 3 alkyl) 2 , and —(CR 10 R 11 ) 0-3 NR 12 R 13 ; and

R 12 , and R 13 are independently selected from H, —C 1 -C 6 alkyl, aryl, heteroaryl, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), and —CON(C 1 -C 6 alkyl) 2 .

7. The compound of claim 6 , wherein one or more of R 1 , R 2 , R 3 , and R 4 is halomethyl.

8. The compound of claim 6 , wherein R 1 is H, and R 2 is —C 1 -C 3 alkoxy; or R 1 is F, Cl, or Br, and R 2 is —CF 3 or —CHF 2 .

9. The compound of claim 6 , wherein A is S (sulfur); X is N (nitrogen); R 1 is F, Cl, or Br; and R 2 is —C 1 -C 3 alkoxy.

10. The compound of claim 6 , wherein

R 3 is —C 1 -C 3 alkyl; and R 4 is H, or

R 3 is —C 1 -C 3 alkyl; and R 4 is —(CR 10 R 11 ) 0-3 NR 12 R 13 .

11. A compound of Formula I:

or a pharmaceutically acceptable salt thereof, wherein

A is O (oxygen) or S (sulfur);

X is CH or N (nitrogen);

M=1 or 2;

each occurrence of R 1 and R 2 is independently selected from H, halo, —CN, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, —OH, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, —NO 2 , —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), and —CON(C 1 -C 6 alkyl) 2 ; or R 1 and R 2 are on adjacent carbons and taken together with the carbons to which they are attached form a 5-6 member monocylic ring system comprising one or two oxygen atoms, wherein the ring system is optionally substituted with one or more F;

R 3 and R 4 taken together with the carbons to which they are attached form a monocylic ring system, having the following structure:

D is O (oxygen), S (sulfur), —SO—, —SO 2 —, or —N—R 9 —;

m and n are independently 0-4, with the proviso that the sum of m and n is 1-5 when D is O (oxygen), S (sulfur), —SO, —SO 2 , —N—R 9 ;

R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are independently selected from H, F, —C 1 -C 6 alkyl, —C 1 -C 6 haloalkyl, —OH, —C 1 -C 6 alkoxy, —C 1 -C 6 haloalkoxy, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), and —CON(C 1 -C 6 alkyl) 2 ; and

R 9 , R 12 , and R 13 are independently selected from H, —C 1 -C 6 alkyl, aryl, heteroaryl, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 6 alkyl) 2 , —CONH(C 1 -C 6 alkyl), and —CON(C 1 -C 6 alkyl) 2 .

12. The compound of claim 11 , wherein R 1 is H, and R 2 is C 1 -C 6 alkoxy; or R 1 is F, Cl, or Br, and R 2 is —CF 3 or —CHF 2 .

13. The compound of claim 12 , wherein A is S (sulfur); and X is N (nitrogen).

14. The compound of claim 12 , wherein R 3 is —C 1 -C 6 alkyl; and R 4 is —(CR 10 R 11 ) 0-3 NR 12 R 13 .

15. A compound of Formula I:

or a pharmaceutically acceptable salt thereof, wherein

A is O (oxygen) or S (sulfur);

X is CH or N (nitrogen);

M=1 or 2;

each occurrence of R 1 and R 2 is independently selected from H, halo, aryl, heteroaryl, —(C 1 -C 3 alkyl) aryl, —(C 1 -C 3 alkyl) heteroaryl, heterocycle, —CN, C 1 -C 3 alkyl, C 1 -C 3 thioalkyl, C 1 -C 3 thiohaloalkyl, C 1 -C 3 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, —OH, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, —NO 2 , —SO 2 C 1 -C 6 alkyl, —SOC 1 -C 3 alkyl, —SO 2 NH(C 1 -C 3 alkyl), —SO 2 N(C 1 -C 3 alkyl) 2 , —CONH(C 1 -C 3 alkyl), —CON(C 1 -C 3 alkyl) 2 , —C(O)O(C 1 -C 3 alkyl), —C(O)O(C 1 -C 3 alkyl)aryl, —OC(O)(C 1 -C 3 alkyl), —OC(O)(C 1 -C 3 alkyl)aryl, —SO 2 NH 2 , —CONH 2 , —CO 2 H, —COH, —NH 2 , C 1 -C 3 alkylamino, di-C 1 -C 3 alkylamino, —N 3 , cyanate, isocyanate, thiocyanate, isothiocyanate, —(C 2 -C 6 alkenyl)O(C 1 -C 3 alkyl), —(C 1 -C 3 alkyl)O(C 1 -C 3 alkyl), —(C 1 -C 3 alkyl)O(C 1 -C 3 alkyl)O(C 1 -C 3 alkyl), aryloxy, arylthio, —CO(C 1 -C 3 alkyl), —CO(aryl), —CO(heteroaryl), and —CO(heterocycle);

or R 1 and R 2 are on adjacent carbons and taken together with the carbons to which they are attached form a 5-6 member saturated or unsaturated monocylic ring system comprising one or two oxygen atoms, wherein the ring system is optionally substituted with one or more F;

R 3 and R 4 taken together with the carbons to which they are attached form a monocylic ring system, having the following structure:

D is O (oxygen), S (sulfur), —SO—, —SO 2 —, or —N—R 9 —;

m and n are independently 0-4, with the proviso that the sum of m and n is 1-5 when D is O (oxygen), S (sulfur), —SO—, —SO 2 —, —N—R 9 ;

R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are independently selected from H, F, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, —OH, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, —SO 2 C 1 -C 6 alkyl, —SO 2 N(C 1 -C 3 alkyl) 2 , —CONH(C 1 -C 3 alkyl), and —CON(C 1 -C 3 alkyl) 2 ; and

R 9 , R 12 , and R 13 are independently selected from H, C 1 -C 3 alkyl, aryl, heteroaryl, —SO 2 C 1 -C 3 alkyl, —SO 2 N(C 1 -C 3 alkyl) 2 , —CONH(C 1 -C 3 alkyl), and —CON(C 1 -C 3 alkyl) 2 .

16. The compound of claim 15 , wherein R 1 is H, and R 2 is C 1 -C 3 alkoxy; or R 1 is F, Cl, or Br, and R 2 is —CF 3 or —CHF 2 .

17. The compound of claim 16 , wherein A is S (sulfur); and X is N (nitrogen).

18. The compound of claim 16 , wherein R 3 is C 1 -C 3 alkyl; and R 4 is —(CR 10 R 11 ) 0-3 NR 12 R 13 .

19. A compound selected from the group consisting of Examples 31, 33, 34, 35, 36, 38, 39, 44, 51, 55, 61, 62, 63, 69, 105, 109, 135 and 141, or a pharmaceutically acceptable salt thereof.

20. A pharmaceutical composition comprising a compound of claim 1 ; and a pharmaceutically acceptable carrier.

Assignments (3)
MERGER Recorded Dec 2, 2021
From: DART NEUROSCIENCE (CAYMAN) LTD.
To: DART NEUROSCIENCE LLC
Reel/Frame 058275/0272 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 7, 2016
From: BRANSTETTER, BRYAN; BREITENBUCHER, JAMES; DYCK, BRIAN; GOMEZ, LAURENT; HUDSON, ANDREW RICHARD; MARRONE, TAMI JO; PETERS, MARCO; VICKERS, TROY; WEINHOUSE, MICHAEL I.
To: DART NEUROSCIENCE, LLC
Reel/Frame 040593/0577 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 7, 2016
From: DART NEUROSCIENCE, LLC
To: DART NEUROSCIENCE CAYMAN (LTD)
Reel/Frame 040593/0637 →
Continuity (3)
Division 13920974 · Jun 18, 2013
Provisional Application 61661091 · Jun 18, 2012
Related Publication 20160075719A1 · Mar 17, 2016