Chemical Properties
White Solid
Usage
Olaparib is a potent poly(ADP-ribose) polymerase (PARP) inhibitor. Olaparib has been shown to induce significant killing of ATM-deficient lymphoid tumor cells in vitro and in vivo. Recent studies show
that Olaparib increases radiosensitivity of a lung tumor xenograft, making it a potential candidate for use in combination with radiotherapy.
Uses
Olaparib is a potent poly(ADP-ribose) polymerase (PARP) inhibitor. Olaparib has been shown to induce significant killing of ATM-deficient lymphoid tumor cells in vitro and in vivo. Recent studies show
that Olaparib increases radiosensitivity of a lung tumor xenograft, making it a potential candidate for use in combination with radiotherapy.
Definition
ChEBI: A member of the class of N-acylpiperazines obtained by formal condensation of the carboxy group of 2-fluoro-5-[(4-oxo-3,4-dihydrophthalazin-1-yl)methyl]benzoic acid with the free amino group of N-(cyclpropylcarbonyl)pi
erazine; used to treat advanced ovarian cancer.
Uses
Many of the products generated by alkylating agents on DNA can be efficiently repaired by normal base excision repair (BER). Some poly(ADP-ribose) polymerases (PARPs) assist in the repair of single-strand DNA nicks, an important step in BER. Olaparib is a potent inhibitor of PARP1 and PARP2 (IC50 = 5 and 1 nM, respectively) but is less effective against the PARP tankyrase-1 (IC50 = 1.5 μM). It can be used in cells and in animals, alone or in combination therapy with alkylating agents, to block BER and increase cancer cell death.[Cayman Chemical]
Description
Olaparib, marketed by AstraZeneca under the brand name Lynparza
, was approved in the USA in December 2014 as a targeted,
single-agent therapy for the treatment of germline BRCA-mediated
advanced ovarian cancer.Olaparib, originally developed by
KuDOS pharmaceuticals and later by AstraZeneca, functions as a
poly ADP ribose polymerase inhibitor and has been specifically
approved for patients who have received three or more treatments
of chemotherapy. In clinical trials, the drug prolonged progression-
free survival for patients suffering from platinum-sensitive
recurrent serous ovarian cancer. Olaparib is also currently in various phases of investigation for treatment of breast,
gastric, prostate, pancreatic and non-small cell lung cancer.
History
Olaparib, the first approved small molecule PARPi, is utilized for the treatment of germline BRCA-mutated ovarian and breast cancers. Olaparib was discovered by Professor Sir Steve Jackson, it was developed and first dosed into patients by the UK-based biotechnology company, KuDOS Pharmaceuticals, that was founded by Stephen Jackson of Cambridge University, UK. Since KuDOS was acquired by AstraZeneca in 2006, the drug has undergone clinical development by AstraZeneca and Merck & Co.
Biological Activity
Many of the products generated by alkylating agents on DNA can be efficiently repaired by normal base excision repair (BER). Some poly(ADP-ribose) polymerases (PARPs) assist in the repair of single-strand DNA nicks, an important step in BER. Olaparib is a potent inhibitor of PARP1 and PARP2 (IC50 = 5 and 1 nM, respectively) but is less effective against the PARP tankyrase-1 (IC50 = 1.5 μM). It can be used in cells and in animals, alone or in combination therapy with alkylating agents, to block BER and increase cancer cell death.[Cayman Chemical]
Clinical Use
Human poly (ADP-ribose) polymerase enzymes
inhibitor:
Treatment of platinum-sensitive relapsed BRCAmutated high grade serous epithelial ovarian,
fallopian tube, or primary peritoneal cancer
Synthesis
This optimized synthesis begins with
reaction of commercially available dimethyl phosphite and 2-carboxybenzaldehyde
(201) to generate the corresponding
phosphonate ester in 95% yield and 95% purity after aqueous
workup.190 Addition of aldehyde 202 to this phosphonate ester
intermediate in the presence of triethylamine led to formation of
olefins 203a/203b in 96% yield as a 1:1 mixture of E/Z isomers.
From olefins 203a/203b, a one-pot, three-step sequence was next
performed to provide access to dihydrophthalazinyl acid 204. First,
lactone ring-opening and nitrile hydrolysis was facilitated by reaction
with aqueous sodium hydroxide under elevated temperatures,
allowing for subsequent in situ formation of the corresponding
dihydrophthalazine intermediate after addition of hydrazine
hydrate. Acidification and precipitation of product with 2 N HCl
led to isolation of the desired material in 77% yield and 96% purity
after filtration. Further coupling of carboxylic acid 204 with Bocpiperazine
(205) (HBTU, DIPEA, DMA) and subsequent removal of
the carbamate with HCl/EtOH provided intermediate 206 in 46%
yield from 204, relying on a pH-controlled workup procedure to
enable isolation of material in high purity (94%) without requiring
chromatography. The final step of the olaparib synthesis was
completed via treatment of piperazine 206 with cyclopropane carbonyl
chloride (207) and triethylamine, leading to isolation of olaparib
in 90% yield and 99.3% purity after distillation.

Metabolism
In vitro, CYP3A4 was shown to be the main enzyme
responsible for the metabolism of olaparib. The majority
of the metabolism was due to oxidation reactions with
a number of the components produced undergoing
subsequent glucuronide or sulfate conjugation.
Following a single dose of [14C]-olaparib, approximately 86%
of the dose was recovered within a 7-day collection period,
approximately 44% via the urine and 42% via the faeces. The
majority of olaparib was excreted as metabolites.
Mode of action
Olaparib is a small molecule inhibitor of the nuclear enzyme poly(ADP-ribose) polymerase (PARP) with potential chemosensitizing, radiosensitizing, and antineoplastic activities. Olaparib selectively binds to and inhibits PARP, inhibiting PARP-mediated repair of single strand DNA breaks; PARP inhibition may enhance the cytotoxicity of DNA-damaging agents and may reverse tumor cell chemoresistance and radioresistance. PARP catalyzes post-translational ADP-ribosylation of nuclear proteins and can be activated by single-stranded DNA breaks.
References
1) Menear?et al. (2008),?4-[3-(4-Cyclopropanecarbonylpiperazine-1-carbonyl)-4-fluorobenzyl]-2H-phthalazin-1-one: a novel bioavailable inhibitor of poly(ADP-ribose)polymerase-1;? J. Med. Chem.,?51?6581
2) Rottenberg?et al. (2008),?High sensitivity of BRCA1-deficient mammary tumors to the PARP inhibitor AZD2281 alone and in combination with platinum drugs; Proc. Natl. Acad. Sci. USA,?105?17079
3) Avila-Arroyo?et al. (2015),?Synergistic effect of Trabectedin and Olaparib combination regimen in breast cancer cell lines; J. Breast Cancer,?18?329
4) Xu?et al. (2015),?Combined olaparib and oxaliplatin inhibits tumor proliferation and induces G2/M arrest and γ-H2AX foci formation in colorectal cancer; Onco. Targets Ther.,?8?3047
5) Ghonim?et al. (2015),?PARP is activated in human asthma and its inhibition by olaparib blocks house dust mite-induced disease in mice; Clin. Sci.(Lond),?129?951