US2021137940A1PendingUtilityA1

Pyrrolobenzodiazepine-anti-psma antibody conjugates

61
Assignee: MEDIMMUNE LTDPriority: Oct 12, 2012Filed: Aug 6, 2020Published: May 13, 2021
Est. expiryOct 12, 2032(~6.2 yrs left)· nominal 20-yr term from priority
C07D 519/00C07D 487/04A61K 47/6855C07D 403/12A61P 43/00A61P 39/00A61P 35/02A61K 47/68035A61K 31/551A61K 47/6869A61P 35/00C07K 2317/56A61K 45/06C07K 2317/24C07K 16/18
61
PatentIndex Score
0
Cited by
0
References
0
Claims

Abstract

Conjugates of an antibody that binds to PSMA with PBD dimers.

Claims

exact text as granted — not AI-modified
1 .- 115 . (canceled) 
     
     
         116 . A conjugate of formula L-(D L ) p , where D L  is of formula I or II: 
       
         
           
           
               
               
           
         
         wherein: 
         L is an antibody (Ab) which binds to PSMA, the antibody comprising a VH domain having the amino acid sequence according to any one of SEQ ID NOs. 1, 2, 3, 4, 5, 6, or 7, optionally further comprising a VL domain having the amino acid sequence according to any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14; 
         when there is a double bond present between C2′ and C3′, R 12  is selected from the group consisting of: 
         (ia) C 5-10  aryl group, optionally substituted by one or more substituents selected from: halo, nitro, cyano, ether, carboxy, ester, C 1-7  alkyl, C 3-7  heterocyclyl and bis-oxy-C 1-3  alkylene; 
         (ib) C 1-5  saturated aliphatic alkyl; 
         (ic) C 3-6  saturated cycloalkyl; 
         (id) 
       
       
         
           
           
               
               
           
         
       
       wherein each of R 21 , R 22  and R 23  are independently selected from H, C 1-3  saturated alkyl, C 2-3  alkenyl, C 2-3  alkynyl and cyclopropyl, where the total number of carbon atoms in the R 12  group is no more than 5;
 (ie) 
 
       
         
           
           
               
               
           
         
       
       wherein one of R 25a  and R 25b  is H and the other is selected from: phenyl, which phenyl is optionally substituted by a group selected from halo, methyl, methoxy; pyridyl; and thiophenyl; and
 (if) 
 
       
         
           
           
               
               
           
         
       
       where R 24  is selected from: H; C 1-3  saturated alkyl; C 2-3  alkenyl; C 2-3  alkynyl; cyclopropyl; phenyl, which phenyl is optionally substituted by a group selected from halo, methyl, methoxy; pyridyl; and thiophenyl;
 when there is a single bond present between C2′ and C3′, 
 R 12  is 
 
       
         
           
           
               
               
           
         
       
       where R 26a  and R 26b  are independently selected from H, F, C 1-4  saturated alkyl, C 2-3  alkenyl, which alkyl and alkenyl groups are optionally substituted by a group selected from C 1-4  alkyl amido and C 1-4  alkyl ester; or, when one of R 26a  and R 26b  is H, the other is selected from nitrile and a C 1-4  alkyl ester;
 R 6  and R 9  are independently selected from H, R, OH, OR, SH, SR, NH 2 , NHR, NRR′, nitro, Me 3 Sn and halo; 
 where R and R′ are independently selected from optionally substituted C 1-12  alkyl, C 3-20  heterocyclyl and C 5-20  aryl groups; 
 R 7  is selected from H, R, OH, OR, SH, SR, NH 2 , NHR, NHRR′, nitro, Me 3 Sn and halo; 
 R″ is a C 3-12  alkylene group, which chain may be interrupted by one or more heteroatoms, e.g. O, S, NR N2  (where R N2  is H or C 1-4  alkyl), and/or aromatic rings, e.g. benzene or pyridine; 
 Y and Y′ are selected from O, S, or NH; 
 R 6′ , R 7′ , R 9′  are selected from the same groups as R 6 , R 7  and R 9  respectively; 
 R L1′  is a linker for connection to the antibody (Ab); 
 R 11a  is selected from OH, OR A , where R A  is C 1-4  alkyl, and SO z M, where z is 2 or 3 and M is a monovalent pharmaceutically acceptable cation; 
 R 20  and R 21  either together form a double bond between the nitrogen and carbon atoms to which they are bound or; 
 R 20  is selected from H and R C , where R C  is a capping group; 
 R 21  is selected from OH, OR A  and SO z M; 
 when there is a double bond present between C2 and C3, R 2  is selected from the group consisting of: 
 (ia) C 5-10  aryl group, optionally substituted by one or more substituents selected from the group comprising: halo, nitro, cyano, ether, carboxy, ester, C 1-7  alkyl, C 3-7  heterocyclyl and bis-oxy-C 1-3  alkylene; 
 (ib) C 1-5  saturated aliphatic alkyl; 
 (ic) C 3-6  saturated cycloalkyl; 
 (id) 
 
       
         
           
           
               
               
           
         
       
       wherein each of R 11 , R 12  and R 13  are independently selected from H, C 1-3  saturated alkyl, C 2-3  alkenyl, C 2-3  alkynyl and cyclopropyl, where the total number of carbon atoms in the R 2  group is no more than 5;
 (ie) 
 
       
         
           
           
               
               
           
         
       
       wherein one of R 15a  and R 15b  is H and the other is selected from: phenyl, which phenyl is optionally substituted by a group selected from halo, methyl, methoxy; pyridyl; and thiophenyl; and
 (if) 
 
       
         
           
           
               
               
           
         
       
       where R 14  is selected from: H; C 1-3  saturated alkyl; C 2-3  alkenyl; C 2-3  alkynyl; cyclopropyl; phenyl, which phenyl is optionally substituted by a group selected from halo, methyl, methoxy; pyridyl; and thiophenyl;
 when there is a single bond present between C2 and C3, 
 R 2  is 
 
       
         
           
           
               
               
           
         
       
       where R 16a  and R 16b  are independently selected from H, F, C 1-4  saturated alkyl, C 2-3  alkenyl, which alkyl and alkenyl groups are optionally substituted by a group selected from C 1-4  alkyl amido and C 1-4  alkyl ester; or, when one of R 16a  and R 16b  is H, the other is selected from nitrile and a C 1-4  alkyl ester;
 R 22  is of formula Ia, formula IIIb or formula IIIc: 
 (a) 
 
       
         
           
           
               
               
           
         
         where A is a C 5-7  aryl group, and either 
         (i) Q 1  is a single bond, and Q 2  is selected from a single bond and —Z—(CH 2 ) n —, where Z is selected from a single bond, O, S and NH and n is from 1 to 3; or 
         (ii) Q 1  is —CH═CH—, and Q 2  is a single bond; 
         (b) 
       
       
         
           
           
               
               
           
         
         where; 
         R C1 , R C2  and R C3  are independently selected from H and unsubstituted C 1-2  alkyl; 
         (c) 
       
       
         
           
           
               
               
           
         
         where Q is selected from O—R L2′ , S—R L2′  and NR N —R L2′ , and R N  is selected from H, methyl and ethyl 
         X is selected from the group comprising: O—R L2′ , S—R L2′ , CO 2 —R L2′ , CO—R L2′ , NH—C(═O)—R L2′ , NHNH—R L2′ , CONHNH—R L2′ , 
       
       
         
           
           
               
               
           
         
       
       NR N R L2′ , wherein R N  is selected from the group comprising H and C 1-4  alkyl;
 R L2′  is a linker for connection to the antibody (Ab); 
 R 10  and R 11  either together form a double bond between the nitrogen and carbon atoms to which they are bound or; 
 R 10  is H and R 11  is selected from OH, OR A  and SO z M; 
 R 30  and R 31  either together form a double bond between the nitrogen and carbon atoms to which they are bound or; 
 R 30  is H and R 31  is selected from OH, OR A  and SO z M. 
 
     
     
         117 . The conjugate according to  claim 116 , wherein R 7  is a C 1-4  alkyloxy group. 
     
     
         118 . The conjugate according to  claim 116 , wherein Y is O and R″ is C 3-7  alkylene. 
     
     
         119 . The conjugate according to  claim 116 , wherein R 6  and R 9  are H. 
     
     
         120 . The conjugate according to  claim 116 , wherein there is a double bond between C2′ and C3′, and R 12  is:
 (a) a C 5-7  aryl group, which may bear one to three substituent groups selected from methoxy, ethoxy, fluoro, chloro, cyano, bis-oxy-methylene, methyl-piperazinyl, morpholino and methyl-thiophenyl; or 
 (b) methyl, ethyl or propyl; or 
 (c) cyclopropyl; or 
 (d) a group of formula: 
 
       
         
           
           
               
               
           
         
       
       wherein the total number of carbon atoms in the R 12  group is no more than 4; or
 (e) the group: 
 
       
         
           
           
               
               
           
         
       
       or
 (f) a group of formula: 
 
       
         
           
           
               
               
           
         
       
       wherein R 24  is selected from H and methyl. 
     
     
         121 . The conjugate according to  claim 116 , wherein there is a single bond between C2′ and C3′, R 12  is 
       
         
           
           
               
               
           
         
       
       and:
 (a) R 26a  and R 26b  are both H; or 
 (b) R 26a  and R 26b  are both methyl; or 
 (c) one of R 26a  and R 26b  is H, and the other is selected from C 1-4  saturated alkyl, C 2-3  alkenyl, which alkyl and alkenyl groups are optionally substituted. 
 
     
     
         122 . The conjugate according to  claim 116 , wherein there is a double bond between C2 and C3, and R 2  is:
 (a) a C 5-7  aryl group which may bear one to three substituent groups selected from methoxy, ethoxy, fluoro, chloro, cyano, bis-oxy-methylene, methyl-piperazinyl, morpholino and methyl-thiophenyl; or   (b) methyl, ethyl or propyl; or   (c) cyclopropyl; or   (d) a group of formula:   
       
         
           
           
               
               
           
         
       
       wherein the total number of carbon atoms in the R 2  group is no more than 4; or
 (e) the group: 
 
       
         
           
           
               
               
           
         
       
       or
 (f) a group of formula: 
 
       
         
           
           
               
               
           
         
       
       wherein R 14  is selected from H and methyl. 
     
     
         123 . The conjugate according to  claim 116 , wherein there is a single bond between C2 and C3, R 2  is 
       
         
           
           
               
               
           
         
       
       and:
 (a) R 16a  and R 16b  are both H; or 
 (b) R 16a  and R 16b  are both methyl; or 
 (c) one of R 16a  and R 16b  is H, and the other is selected from C 1-4  saturated alkyl, C 2-3  alkenyl, which alkyl and alkenyl groups are optionally substituted. 
 
     
     
         124 . The conjugate according to  claim 116 , wherein R 20  is R C , wherein R C  is a group: 
       
         
           
           
               
               
           
         
         where the asterisk indicates the point of attachment to the N10 position, G 2  is a terminating group, L 3  is a covalent bond or a cleavable linker L 1 , L 2  is a covalent bond or together with OC(═O) forms a self-immolative linker. 
       
     
     
         125 . The conjugate according to  claim 116 , wherein
 (a) R 22  is of formula IIIa, and A is phenyl, Q 1  is a single bond, and Q 2  is a single bond; or   (b) R 22  is of formula IIIb, and R C1 , R C2  and R C3  are all H;   and X is NH—R L2′ .   
     
     
         126 . The conjugate according to  claim 116 , wherein R 6′ , R 7′ , R 9′ , and Y′ are the same as R 6 , R 7 , R 9 , and Y. 
     
     
         127 . The conjugate according to  claim 116 , wherein L-R L1′  or L-R L2′  is a group: 
       
         
           
           
               
               
           
         
         where the asterisk indicates the point of attachment to the PBD, Ab is the antibody, L 1  is a cleavable linker, A is a connecting group connecting L 1  to the antibody, L 2  is a covalent bond or together with —OC(═O)— forms a self-immolative linker. 
       
     
     
         128 . The conjugate according to  claim 127 , wherein the group —X 1 —X 2 — in dipeptide, —NH—X 1 —X 2 —CO—, is selected from:
 -Phe-Lys-, 
 -Val-Ala-, 
 -Val-Lys-, 
 -Ala-Lys-, 
 -Val-Cit-. 
 
     
     
         129 . The conjugate according to  claim 127 , wherein C(═O)O and L 2  together form the group: 
       
         
           
           
               
               
           
         
         where the asterisk indicates the point of attachment to the PBD, the wavy line indicates the point of attachment to the linker L 1 , Y is NH, O, C(═O)NH or C(═O)O, and n is 0 to 3. 
       
     
     
         130 . A conjugate according to  claim 116  of formula ConjA: 
       
         
           
           
               
               
           
         
       
     
     
         131 . The conjugate according to  claim 116 , wherein the antibody comprises a VH domain paired with a VL domain, the VH and VL domains having amino acid sequences selected from the group consisting of:
 SEQ ID NO. 1 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14;   SEQ ID NO. 2 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14;   SEQ ID NO. 3 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14;   SEQ ID NO. 4 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14;   SEQ ID NO. 5 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14;   SEQ ID NO. 6 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14; and   SEQ ID NO. 7 paired with any one of SEQ ID NOs. 8, 9, 10, 11, 12, 13, or 14.   
     
     
         132 . The conjugate according to  claim 131 , wherein the paired VH and VL domains have the sequences of:
 SEQ ID NO. 1 paired with SEQ ID NO. 8, SEQ ID NO. 1 paired with SEQ ID NO. 9, SEQ ID NO. 1 paired with SEQ ID NO. 10, SEQ ID NO. 1 paired with SEQ ID NO. 11, SEQ ID NO. 1 paired with SEQ ID NO. 12, SEQ ID NO. 1 paired with SEQ ID NO. 13, SEQ ID NO. 1 paired with SEQ ID NO. 14, SEQ ID NO. 2 paired with SEQ ID NO. 8, SEQ ID NO. 2 paired with SEQ ID NO. 9, SEQ ID NO. 2 paired with SEQ ID NO. 10, SEQ ID NO. 2 paired with SEQ ID NO. 11, SEQ ID NO. 2 paired with SEQ ID NO. 12, SEQ ID NO. 2 paired with SEQ ID NO. 13, SEQ ID NO. 2 paired with SEQ ID NO. 14, SEQ ID NO. 3 paired with SEQ ID NO. 8, SEQ ID NO. 3 paired with SEQ ID NO. 9, SEQ ID NO. 3 paired with SEQ ID NO. 10, SEQ ID NO. 3 paired with SEQ ID NO. 11, SEQ ID NO. 3 paired with SEQ ID NO. 12, SEQ ID NO. 3 paired with SEQ ID NO. 13, SEQ ID NO. 3 paired with SEQ ID NO. 14, SEQ ID NO. 4 paired with SEQ ID NO. 8, SEQ ID NO. 4 paired with SEQ ID NO. 9, SEQ ID NO. 4 paired with SEQ ID NO. 10, SEQ ID NO. 4 paired with SEQ ID NO. 11, SEQ ID NO. 4 paired with SEQ ID NO. 12, SEQ ID NO. 4 paired with SEQ ID NO. 13, SEQ ID NO. 4 paired with SEQ ID NO. 14, SEQ ID NO. 5 paired with SEQ ID NO. 8, SEQ ID NO. 5 paired with SEQ ID NO. 9, SEQ ID NO. 5 paired with SEQ ID NO. 10, SEQ ID NO. 5 paired with SEQ ID NO. 11, SEQ ID NO. 5 paired with SEQ ID NO. 12, SEQ ID NO. 5 paired with SEQ ID NO. 13, SEQ ID NO. 5 paired with SEQ ID NO. 14, SEQ ID NO. 6 paired with SEQ ID NO. 8, SEQ ID NO. 6 paired with SEQ ID NO. 9, SEQ ID NO. 6 paired with SEQ ID NO. 10, SEQ ID NO. 6 paired with SEQ ID NO. 11, SEQ ID NO. 6 paired with SEQ ID NO. 12, SEQ ID NO. 6 paired with SEQ ID NO. 13, SEQ ID NO. 6 paired with SEQ ID NO. 14, SEQ ID NO. 7 paired with SEQ ID NO. 8, SEQ ID NO. 7 paired with SEQ ID NO. 9, SEQ ID NO. 7 paired with SEQ ID NO. 10, SEQ ID NO. 7 paired with SEQ ID NO. 11, SEQ ID NO. 7 paired with SEQ ID NO. 12, SEQ ID NO. 7 paired with SEQ ID NO. 13, or SEQ ID NO. 7 paired with SEQ ID NO. 14.   
     
     
         133 . The conjugate according to  claim 116 , wherein the antibody is an intact, humanised, deimmunized, or resurfaced antibody. 
     
     
         134 . The conjugate according to  claim 116 , wherein the drug loading (p) of drugs (D) to antibody (Ab) is an integer from 1 to about 8, or wherein p is 1, 2, 3, or 4. 
     
     
         135 . A pharmaceutical composition comprising the conjugate of  claim 116  and a pharmaceutically acceptable diluent, carrier, or excipient. 
     
     
         136 . The pharmaceutical composition of  claim 135 , further comprising a therapeutically effective amount of a chemotherapeutic agent. 
     
     
         137 . A method of treating cancer comprising administering to a patient the pharmaceutical composition of  claim 136 . 
     
     
         138 . The method of  claim 137 , wherein the patient is administered a chemotherapeutic agent, in combination with the conjugate.

Cited by (0)

No later patents cite this yet.

References (0)

No backward citations on record.