IP Library Granted Patent US 11,352,320
Granted Patent B2
US 11,352,320 · App. 17/057,921 · Granted Jun 7, 2022

Substituted [1.1.1] bicyclo compounds as indoleamine 2,3-dioxygenase inhibitors

Inventors: Shuwen He (Fanwood, NJ); Dane Clausen (Rahway, NJ); Liangqin Guo (Monroe, NJ); Yongxin Han (Needham, MA); Xianhai Huang (Warren, NJ); Alexander Pasternak (Jamaica Plain, MA); Qinglin Pu (Needham, MA); Dong Xiao (Warren, NJ); Li Xiao (Cranbury, NJ); Feng Ye (Scotch Plains, NJ); Hongjun Zhang (Boston, MA)
Assignee: MERCK SHARP & DOHME CORP.
C07C271/14A61P35/00C07D213/74C07D237/34C07D239/42C07D239/94C07D241/20C07D471/04A61K45/06
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Quick Facts
Patent No.
US 11,352,320
App. No.
17/057,921
Granted
Jun 7, 2022
Kind
B2
Abstract

Disclosed herein are compounds of formula (I) which are inhibitors of an IDO enzyme: (I). Also disclosed herein are uses of the compounds in the potential treatment or prevention of an IDO-associated disease or disorder. Also disclosed herein are compositions comprising these compounds. Further disclosed herein are uses of the compositions in the potential treatment or prevention of an IDO-associated disease or disorder.

Claims (159)

1. A compound of formula (I), or a pharmaceutically acceptable salt thereof:

wherein:

X is selected from a bond and —CH(R a )—; where Ra is selected from hydrogen and C 1-6 alkyl;

R b is selected from: (i) hydrogen and (ii) C 1-6 alkyl;

each occurrence of R 1 and R 2 is independently selected from: (i) hydrogen and (ii) C 1-6 alkyl; and

each occurrence of R 3 and R 4 is independently selected from:

(i) aryl, and

(ii) heterocyclyl, wherein the heterocyclyl is selected from furanyl, imidazolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, naphthyridinyl, phthalazinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two atoms;

wherein each of the aryl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

2. The compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein each occurrence of R 1 and R 2 is independently selected from: (i) hydrogen, (ii) methyl and (iii) ethyl.

3. The compound of claim 2 , or a pharmaceutically acceptable salt thereof, wherein R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to three halogens, and

(c) —CN.

4. The compound of claim 2 , or a pharmaceutically acceptable salt thereof, wherein R 3 is phenyl, optionally substituted with a halogen.

5. The compound of claim 2 , or a pharmaceutically acceptable salt thereof, wherein R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from furanyl, imidazolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, naphthyridinyl, phthalazinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two atoms;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

6. The compound of claim 5 , or a pharmaceutically acceptable salt thereof, wherein R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered aromatic heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two carbon atoms

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

7. The compound of claim 2 , or a pharmaceutically acceptable salt thereof, wherein:

R 1 is hydrogen;

R 2 is selected from:

(i) hydrogen,

(ii) methyl, and

(iii) ethyl;

R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN; and

R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered aromatic heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two carbon atoms;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

8. The compound of claim 7 , or a pharmaceutically acceptable salt thereof, wherein:

R 1 is hydrogen;

R 2 is selected from:

(i) methyl, and

(ii) ethyl;

R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen, and

(b) C 1-6 alkyl, optionally substituted with one to four halogens; and

R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from 6,7-dihydro-5H-cyclopenta[d]pyrimidinyl, 1,7-naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl and quinazolinyl;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-4 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

9. The compound of claim 1 of formula (Ia), or a pharmaceutically acceptable salt thereof:

wherein:

R b is selected from (i) hydrogen and (ii) methyl;

R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to three substituents independently selected from:

(a) halogen, and

(b) C 1-6 alkyl, optionally substituted with one to three halogens; and

R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered aromatic heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two carbon atoms;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to three substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to three halogens, and

(c) —CN.

10. The compound of claim 9 , or a pharmaceutically acceptable salt thereof:

wherein:

R b is hydrogen;

R 3 is phenyl, optionally substituted with one to three substituents independently selected from:

(a) halogen, and

(b) C 1-4 alkyl, optionally substituted with one to three halogens; and

R 4 is phenyl, optionally substituted with one to three substituents independently selected from:

(a) halogen, and

(b) C 1-4 alkyl, optionally substituted with one to three halogens.

11. The compound of claim 1 of formula (Ib), or a pharmaceutically acceptable salt thereof:

wherein:

R b is selected from:

(i) hydrogen,

(ii) methyl, and

(iii) ethyl;

R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN; and

R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl, quinazolinyl and a fused bicyclic ring moiety wherein a 6-membered aromatic heterocyclic ring comprising 2 nitrogen atoms and a 5-membered carbocyclic ring are connected through two carbon atoms;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to four substituents independently selected from:

(a) halogen,

(b) C 1-6 alkyl, optionally substituted with one to four halogens, and

(c) —CN.

12. The compound of claim 11 , or a pharmaceutically acceptable salt thereof:

wherein:

R b is hydrogen;

R 3 is selected from:

(i) phenyl, and

(ii) pyridinyl;

wherein each of the phenyl of (i) and pyridinyl of (ii) is optionally substituted with one to three substituents independently selected from:

(a) halogen, and

(b) C 1-4 alkyl, optionally substituted with one to three halogens; and

R 4 is selected from:

(i) phenyl, and

(ii) a heterocyclyl selected from 6,7-dihydro-5H-cyclopenta[d]pyrimidinyl, 1,7-naphthyridinyl, phthalazinyl, pyridinyl, pyrimidinyl and quinazolinyl;

wherein each of the phenyl of (i) and heterocyclyl of (ii) is optionally substituted with one to three substituents independently selected from:

(a) halogen,

(b) C 1-4 alkyl, optionally substituted with one to three halogens, and

(c) —CN.

13. The compound of claim 1 selected from the group consisting of:

N-(4-chlorophenyl)-2-(3-((2-methylpyrimidin-4-yl)amino)bicyclo[1.1.1]pentan-1-yl)propanamide, N-(4-fluorophenyl)-2-(3-(quinazolin-4-ylamino)bicyclo[1.1.1]pentan-1-yl)propanamide, 2-(3-((6-fluoro-2-methylquinazolin-4-yl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide,

2-(3-((2-chloro-6,7-dihydro-5H-cyclopenta[d]pyrimidin-4-yl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide,

N-(4-fluorophenyl)-2-(3-((6-fluoroquinazolin-4-yl)amino)bicyclo[1.1.1]pentan-1-yl)propanamide, N-(4-fluorophenyl)-2-{3-[(1,7-naphthyridin-8-yl)amino]bicyclo[1.1.1]pentan-1-yl}propanamide, N-(4-fluorophenyl)-2-(3-{[3-fluoro-5-(trifluoromethyl)pyridin-2-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[6-methyl-5-(trifluoromethyl)pyridin-2-yl] amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[5-(trifluoromethyl)pyridin-2-yl] amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[6-(trifluoromethyl)pyrimidin-4-yl] amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

2-(3-{[3-cyano-4-(trifluoromethyl)pyridin-2-yl]amino}bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide,

N-(4-fluorophenyl)-2-(3-{[4-(trifluoromethyl)pyridin-2-yl] amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[2-fluoro-4-(trifluoromethyl)pyridin-3-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[3-(trifluoromethyl)pyridin-2-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[3-(trifluoromethyl)pyrazin-2-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[3-fluoro-5-(trifluoromethyl)pyridin-2-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-{3-[(phthalazin-1-yl)amino]bicyclo[1.1.1]pentan-1-yl}propanamide,

N-(4-fluorophenyl)-2-(3-{[2-(trifluoromethyl)pyridin-4-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[2-(trifluoromethyl)pyrimidin-4-yl]amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

N-(4-fluorophenyl)-2-(3-{[6-(trifluoromethyl)pyridin-2-yl] amino}bicyclo[1.1.1]pentan-1-yl)propanamide,

(S)-N-(4-fluorophenyl)-2-(3-((2-(trifluoromethyl)pyridin-4-yl)amino)bicyclo[1.1.1]pentan-1-yl)propanamide,

(S)-2-(3-((3-chlorobenzyl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide, (S)-2-(3-((3-chlorobenzyl)(methyl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide,

(S)-N-(4-fluorophenyl)-2-(3-((3-(trifluoromethyl)benzyl)amino)bicyclo[1.1.1]pentan-1-yl)propanamide,

(S)-N-(4-fluorophenyl)-2-(3-(methyl(3-(trifluoromethyl)benzyl)amino)bicyclo[1.1.1]pentan-1-yl)propanamide,

(S)-2-(3-((3,4-dichlorobenzyl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide, and

(S)-2-(3-((3,4-dichlorobenzyl)(methyl)amino)bicyclo[1.1.1]pentan-1-yl)-N-(4-fluorophenyl)propanamide;

or a pharmaceutically acceptable salt thereof.

14. A pharmaceutical composition comprising a pharmaceutically acceptable carrier and an effective amount of a compound of claim 1 or a pharmaceutically acceptable salt thereof.

Assignments (2)
MERGER Recorded Aug 8, 2022
From: MERCK SHARP & DOHME CORP.
To: MERCK SHARP & DOHME LLC
Reel/Frame 061102/0145 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 23, 2020
From: HE, SHUWEN; CLAUSEN, DANE; GUO, LIANGQIN; HAN, YONGXIN; HUANG, XIANHAI; PASTERNAK, ALEXANDER; PU, QINGLIN; XIAO, DONG; XIAO, LI; YE, FENG; ZHANG, HONGJUN
To: MERCK SHARP & DOHME CORP.
Reel/Frame 054501/0327 →