IP Library Granted Patent US 10,130,630
Granted Patent B2
US 10,130,630 · App. 15/538,976 · Granted Nov 20, 2018

BTK inhibitors

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Patent No.
US 10,130,630
App. No.
15/538,976
Granted
Nov 20, 2018
Kind
B2
Abstract

The present invention provides Bruton's Tyrosine Kinase (Btk) inhibitor compounds according to Formula (I), or pharmaceutically acceptable salts or stereoisomers thereof, or to pharmaceutical compositions comprising these compounds and to their use in therapy. In particular, the present invention relates to the use of Btk inhibitor compounds of Formula (I) in the treatment of Btk mediated disorders.

Claims (73)

1. A compound according to Formula I or a pharmaceutically acceptable salt thereof

wherein:

Ring A is selected from the group consisting of

n is 0, 1 or 2; g is 0 or 1;

W is CH 2 or O;

Z is C or N;

X and Y are independently H or X and Y can come together to form cyclopropyl, cyclobutyl or cyclopentyl,

S and T are independently H, F, OH, OCH 3 , methyl, ethyl or S and T can come together to form cyclopropyl, provided that when Z is C then S and T can come together to form ═O,

M and L are independently H or M and L can come together to form cyclopropyl,

X and T can come together to form a one to three carbon bridge,

wherein one of X and Y, S and T, M and L, and X and T must be a cyclic moiety;

R 1 is selected from the group consisting of hydrogen, triflouromethyl, cyclopropyl, methyl, and cyano;

R 2 is independently selected from the group consisting of methoxy, ethoxy and halogen; and

R 3 is hydrogen, halogen, methyl, ethyl, propyl or isopropyl.

2. The compound according to claim 1 of Formula Ia or a pharmaceutically acceptable salt thereof

wherein:

Ring A is selected from the group consisting of

n is 0, 1 or 2;

S and T are independently H, F, OH, OCH 3 , methyl, ethyl or S and T can come together to form ═O;

R 1 selected from the group consisting of hydrogen, triflouromethyl, cyclopropyl, methyl, and cyano;

R 2 is independently selected from the group consisting of methoxy, ethoxy and halogen; and

R 3 is hydrogen, halogen, methyl, ethyl, propyl or isopropyl.

3. The compound according to claim 1 of Formula Ib or a pharmaceutically acceptable salt thereof

wherein:

Ring A is selected from the group consisting of

n is 0, 1 or 2;

R 1 is selected from the group consisting of hydrogen, triflouromethyl, cyclopropyl, methyl, and cyano;

R 2 is independently selected from the group consisting of methoxy, ethoxy and halogen; and

R 3 is hydrogen, halogen, methyl, ethyl, propyl or isopropyl.

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

4-(8-amino-3-(2-oxooctahydro-1H-cyclopropa[a]indolizin-5-yl)imidazo[1,5-a]pyrazin-1-yl)-3-ethoxy-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(8-amino-3-((6'S,8a′R)-1′,1′-difluoro-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl)-3-ethoxy-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(8-amino-3-((6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl)-3-ethoxy-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(8-amino-3-((6′R,8a′S)-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl)-3-ethoxy-5-fluoro-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,3′-dioxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,3′-dioxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,3′-dioxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-fluoro-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,3′-dioxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-(4-methylpyridin-2-yl)benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,3′-dioxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-(4-cyclopropylpyridin-2-yl)benzamide;

4-{8-amino-3-[(1′S,6′R,8a′S)-1′-hydroxy-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(1′S,6′R,8a′S)-1′-hydroxy-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-(8-amino-3-((1′S,6′R,8a′S)-1′-hydroxy-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-5-a]pyrazin-1-yl)-3-fluoro-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(8-amino-3-((1′S,6′R,8a′S)-1′-hydroxy-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl)-N-(4-cyclopropylpyridin-2-yl)benzamide;

4-(8-amino-3-((1′S,6′R,8a′S)-1′-methoxy-3′-oxohexahydro-1′H-spiro[cyclopropane-1,2′-5-a]pyrazin-1-yl)-3-ethoxy-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-{8-amino-3-[(5aS,8R,11aR)-11-oxodecahydro-1H-pyrido[1,2-a]pyrrolo[1,2-d]pyrazin-8-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(5aS,8R,11aS)-11-oxodecahydro-1H-pyrido[1,2-a]pyrrolo[1,2-d]pyrazin-8-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(7′R,9a′S)-4′-oxohexahydro-2′H-spiro[cyclobutane-1,3′-pyrido[1,2-a]pyrazin]-7′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′S, 8a′R)-3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-5-fluoro-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-(4-cyclopropylpyridin-2-yl)-3-ethoxy-5-fluorobenzamide;

4-[8-amino-5-fluoro-3-(3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl]-3-ethoxy-5-fluoro-N-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-5-fluoro-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′S, 8a′R)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-methoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-fluoro-5-methoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′S,8a′R)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-5-ethoxy-2-fluoro-N-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzamide;

4-{8-amino-3-[(6′R,8a′S)-1′,1′-difluoro-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-2-chloro-5-ethoxy-N-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]benzamide;

4-{8-amino-3-[(3R,6aR,11aR)-6-oxooctahydro-1H,6H-pyrrolo[1′,2′:4,5]pyrazino[2,1-c] [1,4]oxazin-3-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(3R,6aS,11aR)-6-oxooctahydro-1H,6H-pyrrolo[1′,2′:4,5]pyrazino[2,1-c][1,4]oxazin-3-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-[8-amino-5-chloro-3-(3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl]-N-(4-cyanopyridin-2-yl)-3-ethoxy-5-fluorobenzamide;

4-[8-amino-3-(3′-oxohexahydro-5′H-spiro[cyclopropane-1,1′-indolizin]-6′-yl)imidazo[1,5-a]pyrazin-1-yl]-N-(4-cyanopyridin-2-yl)-3-ethoxy-5-fluorobenzamide;

4-[8-amino-3-(4′-oxohexahydro-2′H,6′H-spiro[cyclopropane-1,1′-pyrido[1,2-a]pyrazin]-7′-yl)imidazo[1,5-a]pyrazin-1-yl]-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(7′R,9a′S)-4′-oxohexahydro-2′H-spiro[cyclopropane-1,3′-pyrido[1,2-a]pyrazin]-7′-yl]imidazo[1,5-a]pyrazin-1-yl}-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(7′R,9a′S)-4′-oxohexahydro-2′H-spiro[cyclopropane-1,3′-pyrido[1,2-a]pyrazin]-7′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-methoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(7′R,9a′S)-2′-ethyl-4′-oxohexahydro-2′H-spiro[cyclopropane-1,3′-pyrido[1,2-a]pyrazin]-7′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(3′R,9a′R)-6′-oxohexahydrospiro[cyclopropane-1,7′-pyrazino[2,1-c][1,4]oxazin]-3′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(3′R,9a′R)-6′-oxohexahydrospiro[cyclopentane-1,7′-pyrazino[2,1-c][ 1,4]oxazin]-3′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide;

4-{8-amino-3-[(6′S, 8a′R)-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-methoxy-N-[4-(trifluoromethyl)pyridin-2-yl]benzamide; and

4-{8-amino-3-[(6′S, 8a′R)-3′-oxohexahydrospiro[cyclopropane-1,2′-indolizin]-6′-yl]imidazo[1,5-a]pyrazin-1-yl}-3-ethoxy-N-[4-(trifluoromethyl)pyri din-2-yl]benzamide;

or a pharmaceutically acceptable salt thereof.

5. A pharmaceutical composition which comprises the compound of claim 1 or a pharmaceutically acceptable salt thereof and one or more pharmaceutically acceptable carriers.

Assignments (4)
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 Sep 6, 2017
From: LIU, JIAN; KOZLOWSKI, JOSEPH A.; ALHASSAN, ABDUL-BASIT; ANAND, RAJAN; BOGA, SOBHANA BABU; GUIADEEN, DEODIAL GUY; YU, WENSHENG; YU, YOUNONG
To: MERCK SHARP & DOHME CORP.
Reel/Frame 043508/0124 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 6, 2017
From: LIU, SHILAN; WU, HAO; YANG, CHUNDAO
To: WUXI APPTEC (SHANGHAI) CO., LTD.
Reel/Frame 043508/0221 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 6, 2017
From: WUXI APPTEC (SHANGHAI) CO., LTD.
To: MERCK SHARP & DOHME CORP.
Reel/Frame 043508/0261 →