IP Library Granted Patent US 8,138,204
Granted Patent B2
US 8,138,204 · App. 11/778,315 · Granted Mar 20, 2012

Stereoisomeric compounds and methods for the treatment of gastrointestinal and central nervous system disorders

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Quick Facts
Patent No.
US 8,138,204
App. No.
11/778,315
Granted
Mar 20, 2012
Kind
B2
Abstract

The subject invention provides stereoisomeric compounds of formula (X): wherein the variables are as defined herein, and compositions for the safe and effective treatment of various gastrointestinal disorders including, but not limited to, gastroparesis, gastroesophageal reflux and related conditions. The compounds of the subject invention are also useful in treating a variety of conditions involving the central nervous system.

Claims (58)

1. A method of treating a gastrointestinal disorder responsive to a 5HT 4 receptor agonist comprising administering to a patient in need of such treatment a therapeutically effective amount of a compound of the formula

and pharmaceutically acceptable salts thereof, wherein

the bonds at positions 3 and 4 are cis relative to each other;

R 1 is halogen;

R 2 is amino, NH(C 1 -C 4 alkyl) or N(C 1 -C 4 alkyl)(C 1 -C 4 alkyl);

R 3 is OH or C 1 -C 4 alkoxy;

R 4 is H or methyl; and

R 5 is —O—C 3 -C 8 cycloalkyl, —O-heterocycloalkyl or heterocycloalkyl, wherein the heterocycloalkyl portion of the —O-heterocycloalkyl or heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, aza-bicyclo-decyl, piperidinyl, piperazinyl, or pyrrolidinyl, wherein

the piperidinyl, piperazinyl, and pyrrolidinyl groups are unsubstituted or substituted at one or two positions with groups that are independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, hydroxyl, hydroxy C 1 -C 4 alkyl, amino, —NH(C 1 -C 4 alkyl), —N(C 1 -C 4 alkyl)(C 1 -C 4 alkyl), —(C 0 -C 6 alkyl)-C(O)R 11 , or NO 2 , and wherein

the aza-bicyclo-octyl, aza-bicyclo-nonyl, and aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl;

R 9 at each occurrence is independently H or C 1 -C 4 alkyl;

R 11 is C 1 -C 6 alkoxy, optionally substituted with 1 or 2 groups that are independently C 1 -C 4 alkoxy, amino, —NH(C 1 -C 6 alkyl), —N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —(C 0 -C 6 alkyl)-C(O)N(R 9 )-heterocycloalkyl, O-heterocycloalkyl, or heterocycloalkyl, wherein the heterocycloalkyl is pyrrolidinyl, piperidinyl, piperazinyl, or morpholinyl, wherein the heterocycloalkyl groups are optionally substituted with 1, 2, or 3 groups that are independently halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, hydroxy C 1 C 6 alkyl, C 1 -C 6 alkoxycarbonyl, —CO 2 H, CF 3 , or OCF 3 ; and

R 20 is C 1 -C 6 alkoxy (preferably C 1 -C 4 alkoxy, more preferably methoxy), or OH.

2. The compound according to claim 1 wherein

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl, wherein the aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl.

3. The compound according to claim 2 wherein

R 1 is chloro;

R 2 is amino;

R 3 is methoxy; and

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl, wherein the aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl.

4. A method according to claim 3 , wherein

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is 1-aza-bicyclo-[2.2.2]oct-3-yl or 8-aza-bicyclo[3.2.1]oct-3-yl, wherein the 1-aza-bicyclo[2.2.2]oct-3-yl or 8-aza-bicyclo[3.2.1]oct-3-yl nitrogen is optionally substituted with methyl or ethyl.

5. A method according to claim 1 , wherein the compound is

(3S)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3S,4R)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate;

(3S)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3R,4S)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate;

(3R)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3R,4S)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate; or

(3R)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3S,4R)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate; or

a pharmaceutically acceptable salt thereof.

6. A method of treating a gastrointestinal disorder selected from the group consisting of gastroesophageal reflux disease (GERD), emesis, dyspepsia, gastroparesis, constipation, intestinal pseudo-obstruction, post-operative ileus comprising administering to a patient in need of such treatment a therapeutically effective amount of a compound of the formula

and pharmaceutically acceptable salts thereof, wherein

the bonds at positions 3 and 4 are cis relative to each other;

R 1 is halogen;

R 2 is amino, NH(C 1 -C 4 alkyl) or N(C 1 -C 4 alkyl)(C 1 -C 4 alkyl);

R 3 is OH or C 1 -C 4 alkoxy;

R 4 is H or methyl; and

R 5 is —O—C 3 -C 8 cycloalkyl, —O-heterocycloalkyl or heterocycloalkyl, wherein the heterocycloalkyl portion of the —O-heterocycloalkyl or heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, aza-bicyclo-decyl, piperidinyl, piperazinyl, or pyrrolidinyl, wherein

the piperidinyl, piperazinyl, and pyrrolidinyl groups are unsubstituted or substituted at one or two positions with groups that are independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, hydroxyl, hydroxy C 1 -C 4 alkyl, amino, —NH(C 1 -C 4 alkyl), —N(C 1 -C 4 alkyl)(C 1 -C 4 alkyl), —(C 0 -C 6 alkyl)-C(O)R 11 , or NO 2 , and wherein

the aza-bicyclo-octyl, aza-bicyclo-nonyl, and aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl;

R 9 at each occurrence is independently H or C 1 -C 4 alkyl;

R 11 is C 1 -C 6 alkoxy, optionally substituted with 1 or 2 groups that are independently C 1 -C 4 alkoxy, amino, —NH(C 1 -C 6 alkyl), —N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —(C 0 -C 6 alkyl)-C(O)N(R 9 )-heterocycloalkyl, O-heterocycloalkyl, or heterocycloalkyl, wherein the heterocycloalkyl is pyrrolidinyl, piperidinyl, piperazinyl, or morpholinyl, wherein the heterocycloalkyl groups are optionally substituted with 1, 2, or 3 groups that are independently halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, hydroxy C 1 C 6 alkyl, C 1 -C 6 alkoxycarbonyl, —CO 2 H, CF 3 , or OCF 3 ; and

R 20 is C 1 -C 6 alkoxy (preferably C 1 -C 4 alkoxy, more preferably methoxy), or OH.

7. The compound according to claim 6 wherein

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl, wherein the aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl.

8. The compound according to claim 7 wherein

R 1 is chloro;

R 2 is amino;

R 3 is methoxy; and

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl, wherein the aza-bicyclo-octyl, aza-bicyclo-nonyl, or aza-bicyclo-decyl nitrogen is optionally substituted with methyl or ethyl.

9. A method according to claim 8 , wherein

R 5 is —O-heterocycloalkyl wherein the heterocycloalkyl is 1-aza-bicyclo-[2.2.2]oct-3-yl or 8-aza-bicyclo[3.2.1]oct-3-yl, wherein the 1-aza-bicyclo[2.2.2]oct-3-yl or 8-aza-bicyclo[3.2.1]oct-3-yl nitrogen is optionally substituted with methyl or ethyl.

10. A method according to claim 9 , wherein the compound is

(3S)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3S,4R)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate;

(3S)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3R,4S)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate;

(3R)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3R,4S)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate; or

(3R)-1-azabicyclo[2.2.2]oct-3-yl 6-{(3S,4R)-4-[(4-amino-5-chloro-2-methoxybenzoyl)amino]-3-methoxypiperidin-1-yl}hexanoate; or

a pharmaceutically acceptable salt thereof.

11. A method according to claim 6 wherein the gastrointestinal disorder is gastroparesis.

12. A method according to claim 10 wherein the gastrointestinal disorder is gastroparesis.

Assignments (10)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 9, 2016
From: ARMETHEON, INC.
To: NARONAPRIDE, LLC
Reel/Frame 040699/0559 →
CHANGE OF NAME Recorded Dec 9, 2016
From: NARONAPRIDE, LLC
To: RENEXXION, LLC
Reel/Frame 040876/0342 →
RELEASE OF SECURITY INTEREST Recorded Feb 6, 2013
From: AYER CAPITAL PARTNERS MASTER FUND, L.P.; MPM BIOVENTURES III, L.P.; MPM BIOVENTURES III-QP, L.P.; MPM BIOVENTURES III GMBH & CO. BETEILIGUNGS KG; MPM BIOVENTURES III PARALLEL FUND, L.P.; AYER CAPITAL PARTNERS KESTREL FUND, L.P.; MPM ASSET MANAGEMENT INVESTORS 2002 BVIII LLC
To: ARYX THERAPEUTICS, INC.
Reel/Frame 029767/0524 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2012
From: IRWIN, IAN; PALME, MONICA; BECKER, CYRUS; DRUZGALA, PASCAL
To: ARYX THERAPEUTICS, INC.
Reel/Frame 028995/0828 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2012
From: ARYX THERAPEUTICS, INC.
To: ARMETHEON, INC.
Reel/Frame 028995/0936 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2012
From: ARYX THERAPEUTICS
To: ARYX THERAPEUTICS, INC.
Reel/Frame 028995/0791 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2012
From: IRWIN, IAN; PALME, MONICA; BECKER, CYRUS
To: ARYX THERAPEUTICS
Reel/Frame 028995/0657 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2012
From: IRWIN, IAN; PALME, MONICA; BECKER, CYRUS; RUBENS, COURTNEY; DRUZGALA, PASCAL
To: ARYX THERAPEUTICS
Reel/Frame 028995/0704 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 4, 2012
From: IRWIN, IAN; PALME, MONICA; BECKER, CYRUS
To: ARYX THERAPEUTICS
Reel/Frame 028894/0453 →
SECURITY AGREEMENT Recorded Oct 18, 2010
From: ARYX THERAPEUTICS, INC.
To: AYER CAPITAL PARTNERS MASTER FUND, L.P.; MPM BIOVENTURES III, L.P.; MPM BIOVENTURES III-QP, L.P.; MPM BIOVENTURES III GMBH & CO. BETEILIGUNGS KG; MPM BIOVENTURES III PARALLEL FUND, L.P.; AYER CAPITAL PARTNERS KESTREL FUND, L.P.; MPM ASSET MANAGEMENT INVESTORS 2002 BVIII LLC
Reel/Frame 025150/0379 →