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WO 2014/028653 Al 20 February 2014 (20.02.2014) P O P C T

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WO 2014/028653 Al 20 February 2014 (20.02.2014) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2014/028653 Al 20 February 2014 (20.02.2014) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07F 9/80 (2006.01) Λ 61Κ 31/282 (2006.01) kind of national protection available): AE, AG, AL, AM, C07F 9/90 (2006.01) A61K 31/285 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, C07F 9/94 (2006.01) A61K 31/29 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, C07F 15/00 (2006.01) A61K 31/295 (2006.01) DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, C07F 15/04 (2006.01) A61P 35/00 (2006.01) HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, (21) International Application Number: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, PCT/US20 13/054999 OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, (22) International Filing Date: SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, 14 August 2013 (14.08.2013) TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (25) Filing Language: English (84) Designated States (unless otherwise indicated, for every (26) Publication Language: English kind of regional protection available): ARIPO (BW, GH, (30) Priority Data: GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, 61/683,03 1 14 August 2012 (14.08.2012) US UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (71) Applicant: NORTHWESTERN UNIVERSITY EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, [US/US]; 633 Clark Street, Evanston, IL 60208 (US). MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, (72) Inventors: MIODRAGOVIC, Denana, U.; 6325 North KM, ML, MR, NE, SN, TD, TG). Sheridan Road, # 1102, Chicago, IL 60660 (US). O'HAL- LORAN, Thomas, V.; 1139 West Lunt Avenue, Chicago, Published: IL 60626 (US). — with international search report (Art. 21(3)) (74) Agent: CELANDER, Daniel, W.; Klintworth & Rozen- — before the expiration of the time limit for amending the blat IP LLC, 850 West Jackson Boulevard, Suite 525, claims and to be republished in the event of receipt of Chicago, IL 60607 (US). amendments (Rule 48.2(h)) (54) Title: ARSENOPLATIN ANTI-CANCER AGENTS (57) Abstract: Disclosed are compound having the structure of formula (I): wherein M is Pt, Pd or Ni; Q is As, Sb or Bi; Z 1 is N; Z2 is O or S; L1 and L2 are independently C(O), C-R 1 or C-R2; X is a Lewis base X and Y 1 and Y 2 are independently oxygen- or sul fur-containing substituents, conjugates containing compounds of formula (I) and their use as chemo therapy agents. 1 (I) 00 o o o ARSENOPLATIN ANTI-CANCER AGENTS CROSS-REFERENCE TO RELATED APPLICATIONS [01] This application claims benefit of priority under 35 U.S.C. 119 to U.S. provisional patent application serial number 61/663,031 filed August 14, 2012, and entitled ARSENOPLATTNS-A NEW CLASS OF ANTI-CANCER AGENTS, the contents of which are herein incorporated by reference in its entirety. BACKGROUND Technical Field [02] The disclosure relates to arsenoplatin and related compounds and methods for their use as chemotherapy agents. Description of Relevant Prior Art [03] Cis-diamminedicUoroplatinum(II) ("Cisplatin") and arsenic trioxide (AS2O3) are highly successful agents for treatment of cancer. Cisplatin is used in combination chemotherapy to treat ovarian, testicular, head, neck, and bladder cancers. Unfortunately, these and other cancers frequently develop resistance to this widely used agent and there are intensive efforts to develop new agents that overcome this resistance. Arsenic trioxide, which was discovered as a traditional Chinese medicine, is a front line treatment for acute promyelocytic leukemia and has also shown preliminary efficacy in the treatment of blood cancers such as multiple myeloma and myelodysplasia syndromes. [04] Both compounds induce apoptotic cell death, but through different pathways. Cisplatin reacts with DNA and causes intra- and inter-strand DNA cross-links. The principal component of aqueous solutions of AS2O3 at pH 7, arsenous acid , at low concentrations reacts with and triggers degradation of key zinc-dependent regulatory proteins and inhibits angiogenesis, migration and invasion. At higher concentrations, arsenous acid triggers apoptosis through pathways that involve elevated levels of reactive oxygen species in mitochondria. [05] When combined, these agents can act synergistically in certain cisplatin sensitive and resistant ovarian and non-small lung carcinoma cells. The only example of a platinum adduct with arsenous acid in the literature emerged in efforts to develop efficient systems for loading AS2O3 into liposomes with aquated forms of cisplatin. BRIEF SUMMARY [06] In a first aspect a compound having the structure of formula (I) is disclosed: wherein M is Pt, Pd or Ni; Q is As, Sb or Bi; Z is N ; Z2 is O or S; L and L2 are independently C(0), C-R 1 or C-R 2;X is a Lewis base; Y1 and Y2 are independently selected from -OR 3, -OR 4, -SR 3 and -^SR4, wherein R 1 and R2 are independently selected from hydrogen, halogen, cyano, keto, ester, ether, thiol, thioether, thioester, imino, Ci-Cio alkyl, Ci-Cio alkenyl, alkynyl, alkoxyl, amino, amidyl, immino, sulfonyl, sulfoxyl, phosphoryl, phosphoryl ester, glycosyl, aryl, C3-C15 cycloalkyl, heteroaryl, and C3- 5 heterocycloalkyl; wherein R and R4 are independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkenyl, alkynyl, alkoxyl, amino, amidyl, immino, sulfonyl, sulfoxyl, phosphoryl, phosphoryl ester, glycosyl, aryl, C3- 5 cycloalkyl, heteroaryl, and C3- 5heterocycloalkyl; wherein the Lewis base can be halogen, N-bonded cyano, nitroso, nitroxyl, N-bonded C1-C10 alkyl, C1-C10 alkenyl, N-bonded C3-C10 cycloalkyl, N-bonded Ci-Cioheteroalkyl, N-bonded C1-C10 heteroalkenyl, N-bonded aryl, N-bonded heteroaryl, N-bonded C3- 5heterocycloalkyl, -NR 5R6, N-bonded ligand, S-bonded cyano, sulfonyl, sulfoxyl, thiol, S-bonded thioether, S-bonded thioester, S-bonded Ci-Cioalkyl, C1-C10 alkenyl, S-bonded C3-C10 cycloalkyl, S-bonded Ci-Cioheteroalkyl, S-bonded C1-C10 heteroalkenyl, S-bonded aryl, S-bonded heteroaryl, S-bonded C3- 5heterocycloalkyl, -^SR5, S-bonded ligand, O-bonded C3-C10 cycloalkyl, O-bonded Ci-Cioheteroalkyl, O-bonded C1-C10 heteroalkenyl, O-bonded aryl, O-bonded heteroaryl, O-bonded C3- 5 heterocycloalkyl, -OR 5, O-bonded carboxylato, O-bonded polycarboxylato, O-bonded carboxylato, O-bonded polycarboxylato, O-bonded carboxylato, O-bonded polycarboxylato, O-bonded ligand, or P-bonded phosphine having formula P(R )3_x(R )x, where x is 0, 1, or 3; 5 6 9 9 wherein R and R are independently selected from hydrogen, O, - C0 2R , -COR , C1-C10 alkyl, C1-C10 alkenyl, aryl, heteroaryl, C3- 5cycloalkyl and C3- 5heterocycloalkyl; wherein R7 and R8 are independently selected from C1-C10 alkyl, C1-C10 alkenyl, aryl, heteroaryl, C3- 5 cycloalkyl and C3-C15 heterocycloalkyl; and wherein R is selected from hydrogen, hydroxyl, halogen, amine, thiol, ether, Ci-Cio alkyl, Ci-Cio alkenyl, aryl, heteroaryl, C3- 5 cycloalkyl and C3-C15 heterocycloalkyl. [07] In a second aspect, conjugate that includes a ligand and a compound having the structure of formula (I) is disclosed: x wherein M is Pt, Pd or Ni; Q is As, Sb or Bi; Z is N ; Z2 is O or S; L and L2 are independently C(0), 1 2 1 2 3 4 3 C-R or C-R ; X is a Lewis base; Y and Y are independently selected from -OR , -OR , -SR and -^SR4, wherein R 1 and R2 are independently selected from hydrogen, halogen, cyano, keto, ester, ether, thiol, thioether, thioester, imino, C1-C10 alkyl, C1-C10 alkenyl, alkynyl, alkoxyl, amino, amidyl, immino, sulfonyl, sulfoxyl, phosphoryl, phosphoryl ester, glycosyl, aryl, C3-C15 cycloalkyl, heteroaryl, and C3- 5 heterocycloalkyl; wherein R and R4 are independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkenyl, alkynyl, alkoxyl, amino, amidyl, immino, sulfonyl, sulfoxyl, phosphoryl, phosphoryl ester, glycosyl, aryl, C3- 5 cycloalkyl, heteroaryl, and C3- 5 heterocycloalkyl; wherein the Lewis base can be halogen, N-bonded cyano, nitroso, nitroxyl, N-bonded C1-C10 alkyl, C1-C10 alkenyl, N-bonded C3-C10 cycloalkyl, N-bonded Ci-Cioheteroalkyl, N-bonded C1-C10 heteroalkenyl, N-bonded aryl, N-bonded heteroaryl, N-bonded C3- 5 heterocycloalkyl, -NR 5R6, N-bonded ligand, S-bonded cyano, sulfonyl, sulfoxyl, thiol, S-bonded thioether, S-bonded thioester, S-bonded Ci-Cioalkyl, C1-C10 alkenyl, S-bonded C3-C10 cycloalkyl, S-bonded Ci-Cioheteroalkyl, S-bonded C1-C10 heteroalkenyl, S-bonded aryl, S-bonded heteroaryl, S-bonded C3- 5 heterocycloalkyl, -^SR5, S-bonded ligand, O-bonded C3-C10 cycloalkyl, O-bonded Ci-Cioheteroalkyl, O-bonded C1-C10 heteroalkenyl, O-bonded aryl, O-bonded heteroaryl, O-bonded C3- 5 heterocycloalkyl, -OR 5, O-bonded carboxylato, O-bonded polycarboxylato, O-bonded ligand, or P-bonded phosphine having formula P(R )3_x(R )x, where x is 0, 1, or 3; 5 6 9 9 wherein R and R are independently selected from hydrogen, O, - C0 2R , -COR , C1-C10 alkyl, C1-C10 alkenyl, aryl, heteroaryl, C3- 5 cycloalkyl and C3-C15 heterocycloalkyl; wherein R7 and R8 are independently selected from Ci-Cio alkyl, -Cioalkenyl, aryl, heteroaryl, C3- 5 cycloalkyl and C3- 5heterocycloalkyl; and wherein R9 is selected from hydrogen, hydroxyl, halogen, amine, thiol, ether, C1-C10 alkyl, C1-C10 alkenyl, aryl, heteroaryl, C3- 5cycloalkyl and C3-C15 heterocycloalkyl.
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