IP Library Granted Patent US 9,388,144
Granted Patent B2
US 9,388,144 · App. 14/553,157 · Granted Jul 12, 2016

Radiolabeled prostate specific membrane antigen inhibitors

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Quick Facts
Patent No.
US 9,388,144
App. No.
14/553,157
Granted
Jul 12, 2016
Kind
B2
Abstract

Compounds according to Formula I and Formula II are potent inhibitors of PSMA activity: Pharmaceutical compositions may include a complex of a radionuclide and a compound of Formula I or Formula II.

Claims (46)

1. A compound represented by formula I

wherein:

X and Y are each independently (CHR 1 ) m or C(O);

W is H or —(CH 2 ) p —U;

L is —C(O)—(C 1 -C 10 )alkylene, —[C(O)—(CH(Z) d )—NH] j NR 2 R 3 , —C(O)—(CHR 1 )—(CH 2 ) p —U—, —(C 5 -C 14 )aryl-(C 1 -C 10 )alkylene, R 6 O-benzylene, —(C 5 -C 14 )heteroaryl-(C 1 -C 10 )alkylene, —C(O)—[(CH 2 ) p —V] n —(CH 2 ) q —C(O)—U or [C(O)—CH(Z) d —NH] t —C(O)—(CHR 1 ) m —(CH 2 ) p —U;

T is selected from the group consisting of: H, —(C 1 -C 10 )alkylene, RC(O)—(C 1 -C 10 )alkylene, NR 2 R 3 —(C 1 -C 10 )alkylene, —(C 5 -C 14 )heteroaryl-(C 1 -C 10 )alkylene and —(C 5 -C 14 )aryl-(C 1 -C 10 )alkylene;

U is selected from the group consisting of: —OR, —COR and —NR 4 R 5 ;

V is selected from the group consisting of U—NH—, —NR 2 — and —NR 2 R 3 ;

Z is —(CH 2 ) p —COOH or —(CH 2 ) p —NR 2 R 3 ;

R, R a and R b are each independently —H, —OH, —(C 1 -C 10 )alkyl, —O(C 1 -C 10 )alkyl, or NHR 2 ;

R 1 and R′″ are each independently —H or —NH 2 ;

R 2 , R 3 , R 4 and R 5 are each independently H, bond, (C 1 -C 10 )alkylene, F, Cl, Br, I, C(O), C(S), —C(S)—NH-benzyl-, —C(O)—NH-benzyl-, —C(O)—(C 1 -C 10 )alkylene, —(CH 2 ) p —NH—C(O)—(CH 2 ) p —, —(CH 2 —CH 2 ) t —NH—C(O)—(CH 2 ) p —, —(CH 2 ) p —COR, —(CH 2 ) p —C(O)NH—C[(CH 2 ) p —COR] 3 , —C[(CH 2 ) p —COR] 3 , or —(CH 2 ) p —(C 5 -C 14 )heteroaryl;

R 6 is —O(CH 2 ) p —(C 5 -C 14 )heteroaryl-(CH 2 ) p —U;

d, j, k, m, n, p and t are each independently 0, 1, 2, 3, 4, 5, or 6; and

with the proviso that where W is —(CH 2 ) 5 — or —CH(NH 2 )—(CH 2 ) 4 —, L is not a —C(O)CH 2 —.

2. The compound of claim 1 , wherein X is (CHR 1 ) m , Y is C(O), W is hydrogen and k is 5.

3. The compound of claim 1 , wherein L is —C(O)CH 2 — and T is hydrogen.

4. The compound of claim 1 , wherein R 1 is hydrogen and m is 2.

5. The compound of claim 1 , wherein L is —C(O)—[(CH 2 ) p —V] n —(CH 2 ) q —C(O)—U or —C(O)—(C 1 -C 10 )alkylene.

6. The compound of claim 5 , wherein L is —C(O)methylene.

7. The compound of claim 5 , wherein L is —C(O)—[(CH 2 ) p —V] n —(CH 2 ) q —C(O)—U and T is hydrogen.

8. The compound of claim 7 , wherein V is NR 2 , n is 2 and q is 1.

9. The compound of claim 7 , wherein U is NR 2 R 3 .

10. The compound of claim 9 , wherein R 2 is hydrogen and R 3 is —(CH 2 ) 2 —NH—C(O)—(CH 2 )—.

11. The compound of claim 1 , wherein L is OR 6 -benzylene and T is —(C 5 -C 14 )heteroaryl-(C 1 -C 10 )alkylene.

12. The compound of claim 11 , wherein the heteroaryl is an imidazole, further substituted with the group —(C 1 -C 10 )alkylene-C(O)—U.

13. The compound of claim 11 , wherein T is selected from the group consisting of

14. The compound of claim 1 , wherein T is.

15. The compound of claim 14 , wherein each R′″ is independently

16. The compound of claim 4 , wherein W is —(CH 2 )—COOH, k is 1, L is —[C(O)—(CH(Z) d )—NH] j —NR 2 R 3 and T is hydrogen.

17. The compound of claim 16 , wherein R 2 is hydrogen, R 3 is —C(O)CH 2 — and j is 4.

18. The compound of claim 4 , wherein W and T are hydrogen, k is 5, and L is [C(O)—CH(Z) d —NH] t —C(O)—(CHR 1 ) m —(CH 2 ) p —U.

19. The compound of claim 18 , wherein Z is —(CH 2 ) 4 —NR 2 R 3 and U is —NR 4 R 5 .

20. The compound of claim 18 , wherein m and t are 1, p is 4 and R 1 is —NH 2 .

21. The compound of claim 19 , wherein R 4 is hydrogen and R 5 is C(O)methylene.

22. The compound of claim 19 , wherein R 2 and R 3 are each independently —(CH 2 ) p —(C 5 -C 14 )heteroaryl.

23. The compound of claim 18 , wherein p is 1 and the heteroaryl is an imidazole, further substituted with the group —(C 1 -C 10 )alkylene-C(O)—U.

24. The compound of claim 1 , which is:

or a pharmaceutically acceptable salt, or ester thereof.

25. A metal complex comprising a radionuclide and the compound of claim 1 .

26. The metal complex of claim 25 , wherein the radionuclide is selected from the group consisting of 111 In, 90 Y, 68 Ga, 64 Cu 153 Gd, 155 Gd, 157 Gd, 157 Fe and 177 Lu.

27. The metal complex of claim 25 , which is:

or a pharmaceutically acceptable salt thereof;

wherein M is 111 In, 90 Y, 68 Ga, 64 Cu, or 177 Lu.

28. A pharmaceutical composition comprising the compound of claim 1 , or a pharmaceutically acceptable salt or ester thereof; and a pharmaceutically acceptable carrier.

29. A pharmaceutical composition comprising the metal complex of claim 25 , or a pharmaceutically acceptable salt or ester thereof; and a pharmaceutically acceptable carrier.

Assignments (4)
RELEASE OF SECURITY INTEREST Recorded Dec 2, 2022
From: WELLS FARGO BANK, N.A.
To: PROGENICS PHARMACEUTICALS, INC.; MOLECULAR INSIGHT PHARMACEUTICALS, INC.; PSMA DEVELOPMENT COMPANY, LLC
Reel/Frame 062047/0915 →
SECURITY INTEREST Recorded Dec 2, 2022
From: LANTHEUS MEDICAL IMAGING, INC.; MOLECULAR INSIGHT PHARMACEUTICALS, INC.; PSMA DEVELOPMENT COMPANY, LLC; PROGENICS PHARMACEUTICALS, INC.
To: CITIZENS BANK, N.A.
Reel/Frame 062047/0960 →
SECURITY AGREEMENT Recorded Aug 19, 2020
From: PROGENICS PHARMACEUTICALS, INC.; MOLECULAR INSIGHT PHARMACEUTICALS, INC.; PSMA DEVELOPMENT COMPANY LLC
To: WELLS FARGO BANK, N.A.
Reel/Frame 053538/0666 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 28, 2016
From: BABICH, JOHN W.; ZIMMERMAN, CRAIG; JOYAL, JOHN L.; LU, GENLIANG
To: MOLECULAR INSIGHT PHARMACEUTICALS
Reel/Frame 038109/0552 →