STAT3 protein degraders
The present disclosure provides compounds represented by Formulae I and IV: wherein R 1a , R 1b , R 2a , R 2b , A, E, Q D , and Q E are as defined in the specification, and the salts and solvates thereof. Compounds of Formula I are degraders of STAT3. Compounds of Formula IV are inhibitors of STAT3. STAT3 degraders and inhibitors are useful for the treatment of cancer and other diseases.
1 . A compound of Formula I:
or a pharmaceutically acceptable salt or solvate thereof, wherein:
R 1a and R 1b are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, and —CH 2 OC(═O)R 1e ;
R 1e is C 1 -C 6 alkyl;
R 2a and R 2b are each fluoro; or
R 2a and R 2b taken together with the carbon atom to which they are attached form a —C(═O)— group;
A is selected from the group consisting of:
G 1 is selected from the group consisting of —O—, —S—, and —NR 17 —;
G 2 is selected from the group consisting of —N═ and —CR 18a ═;
G 3 is selected from the group consisting of —N═ and —CR 18b ═;
R 3 is selected from the group consisting of hydrogen, halo, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, —C(═O)R 3a , and (C 6 -C 14 aryl)C 1 -C 6 alkyl;
R 17 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, (C 6 -C 14 aryl)C 1 -C 6 alkyl, and —C(═O)R 17a ;
R 17a is C 1 -C 4 alkyl;
R 18a and R 18b are each independently selected from the group consisting of hydrogen, halo, and C 1 -C 4 alkyl,
wherein the bond designated with an “*” is attached to —C(═O)-E-Q D ;
E is
wherein the bond of E-8 designated with an “*” is attached to Q D ;
R 3g is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
R 4m is selected from the group consisting of hydrogen, halo, and C 1 -C 4 alkyl;
R 4n is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
R 4o and R 4p are each independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl; or
R 4o and R 4p taken together with the carbon atom to which they are attached form a —C(═O)— group;
Q D is selected from the group consisting of:
X 4 is selected from the group consisting of —CH 2 —, —O—, and —N(R 11d )—; or
X 4 is absent;
v is 0, 1, 2, 3, or 4;
R 12d is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, and (C 6 -C 14 aryl)C 1 -C 6 alkyl;
R 13a is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, optionally substituted C 3 -C 12 cycloalkyl, optionally substituted C 6 -C 14 aryl, (C 6 -C 14 aryl)C 1 -C 6 alkyl, and optionally substituted 5- to 9-membered heteroaryl;
R 13b is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
R 13c is selected from the group consisting of hydrogen and C 1 -C 4 alkyl; or
R 13a and R 13b taken together form a optionally substituted C 3 -C 8 cycloalkyl or optionally substituted 4- to 9-membered heterocyclo; or
R 13b and R 13c taken together form a optionally substituted 4- to 9-membered heterocyclo;
A 2 of Q-6 is selected from the group consisting of —C(R 14b )— and —N—;
R 14b is selected from the group consisting of hydrogen and C 1 -C 3 alkyl;
g is 1, 2, or 3;
h is 1, 2, or 3;
L is -J 1 -Y 1 -J 2 -Y 2 -J 3 -Z—;
J 1 is selected from the group consisting of C 1 -C 12 alkylenyl, 3- to 20-membered heteroalkylenyl, C 4 -C 6 cycloalkylenyl, 4- to 8-membered heterocyclenyl, phenylenyl, and 5- to 9-membered heteroarylenyl; or
J 1 is absent;
Y 1 is selected from the group consisting of —(CH 2 ) m —, —C≡C—, —CH≡CH—, —N(R 16 a)-, —C(═O)—, —S(═O) 2 —, —C(═O)O—, —OC(═O)—, —C(═O)N(R 16b )—, and —N(R 16b ) C(═O)—;
m is 0, 1, 2, or 3;
R 16a is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, and (C 6 -C 14 aryl) C 1 -C 6 alkyl;
R 16b is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
J 2 is selected from the group consisting of C 1 -C 12 alkylenyl, 3- to 20-membered heteroalkylenyl, C 4 -C 6 cycloalkylenyl, 4- to 8-membered heterocyclenyl, phenylenyl, and 5- to 9-membered heteroarylenyl; or
J 2 is absent;
Y 2 is selected from the group consisting of —(CH 2 ) n —, —C≡C—, —CH═CH—, —N(R 16a ′)—, —C(═O)—, —S(═O) 2 —, —C(═O)O—, —OC(═O)—, —C(═O)N(R 16b ′), and —N(R 16b ′) C(═O)—;
n is 0, 1, 2, 3, 4, 5, or 6;
R 16a ′ is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, and (C 6 -C 14 aryl)C 1 -C 6 alkyl;
R 16b ′; is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
J 3 is selected from the group consisting of C 1 -C 12 alkylenyl, 3- to 20-membered heteroalkylenyl, C 4 -C 6 cycloalkylenyl, 4- to 8-membered heterocyclenyl, phenylenyl, and 5- to 9-membered heteroarylenyl; or
J 3 is absent;
Z is selected from the group consisting of —(CH 2 ) d —, —C≡C—, —CH—CH—, —C(═O)—, —O—, —S—, —N(R 16c )—, —C(═O)N(R 16d )—, —N(R 16d ) C(═O)—, —N(R 16e ) C(═O)CH 2 O—,
and —N(R 16f ) C(═O)CH 2 N(R 16g )—;
d is 0, 1, 2, or 3;
R 16c , R 16d , R 16e , R 16f , and R 16g are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, and (C 6 -C 14 aryl)C 1 -C 6 alkyl;
wherein Z is attached to B;
B is selected from the group consisting of:
A 5 is selected from the group consisting of —C(R 19a )═ and —N═;
A 2 of B-1, B-3, and B-4 is selected from the group consisting of —C(R 19b )═ and —N═;
A 3 is selected from the group consisting of —C(R 19c )═ and —N═;
A 4 is selected from the group consisting of —C(R 19 d)═ and —N═;
Z 1 is selected from the group consisting of —CH 2 and —C(—O)—;
R 5a of B-1, B-2, B-3, and B-4 is selected from the group consisting of hydrogen, methyl, and fluoro;
R 5b of B-1, B-2, B-3, and B-4 is selected from the group consisting of hydrogen and methyl;
R 19a , R 19b , R 19c , and R 19d are each independently selected from the group consisting of hydrogen, halo, and C 1-4 alkyl;
R 20 is C 1 -C 6 alkyl;
R 21 is selected from the group consisting of hydrogen and C 1 -C 4 alkyl;
R 22a is selected from the group consisting of C 1 -C 6 alkyl and optionally substituted C 3 -C 6 cycloalkyl;
R 22b is selected from the group consisting of C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl, optionally substituted C 6 -C 14 aryl, and optionally substituted 5- to 14-membered heteroaryl;
R 23 is selected from the group consisting of C 1 -C 6 alkyl and optionally substituted C 3 -C 6 cycloalkyl; and
R 24 is selected from the group consisting of C 1 -C 6 alkyl, optionally substituted C 3 -C 6 cycloalkyl, optionally substituted C 6 -C 14 aryl, and optionally substituted 5- to 14-membered heteroaryl.
2 . The compound of claim 1 , wherein A is selected from the group consisting of:
3 . The compound of claim 2 , wherein A is:
4 . The compound of claim 1 , wherein R 2a and R 2b are each fluoro.
5 . The compound of claim 1 , wherein
E-8 is selected from the group consisting of:
6 . The compound of claim 1 , wherein L is —Y 1 -J 2 -Y 2 -J 3 -Y 2 —, —Y 1 -Y 2 -J 3 Z—, —Y 1 -J 2 -Y 2 —Z—, or —Y 1 -Y 2 —Z—.
7 . The compound of claim 6 , wherein Y 1 is selected from the group consisting of —(CH 2 ) m — and —C(═O)—; m is 1, 2, or 3; Y 2 is —(CH 2 ) n —; n is 1, 2, 3, 4, 5, or 6; and Z is selected from the group consisting of —(CH 2 )—, —C≡C—, and —N(H)—.
8 . The compound of claim 1 , wherein B is B-1, and B-1 is:
or a pharmaceutically acceptable salt or solvate thereof.
9 . The compound of claim 1 , wherein R 1a and R 1b are each hydrogen.
10 . The compound of claim 1 , wherein the compound is selected from:
or a pharmaceutically acceptable salt or solvate thereof.
11 . A pharmaceutical composition comprising the compound of claim 1 , or a pharmaceutically acceptable salt or solvate thereof, and a pharmaceutically acceptable carrier.
12 . The compound of claim 1 , wherein Q-5 is Q-5-1 or Q-5-2:
or a pharmaceutically acceptable salt or solvate thereof.
13 . The compound of claim 12 , wherein X 4 is —CH 2 —and v is 0, or a pharmaceutically acceptable salt or solvate thereof.
14 . The compound of claim 12 , wherein R 12d is hydrogen, or a pharmaceutically acceptable salt or solvate thereof.
15 . The compound of claim 12 , wherein R 13a is selected from the group consisting of optionally substituted C 3 -C 12 cycloalkyl, aralkyl, and optionally substituted phenyl, or a pharmaceutically acceptable salt or solvate thereof.
16 . The compound claim 1 , wherein Q-6 is Q-6-1 or Q-6-2:
or a pharmaceutically acceptable salt or solvate thereof.