Design and synthesis of a folate-receptor targeted diazepine-ring-opened pyrrolobenzodiazepine prodrug conjugate

Bioorg Med Chem Lett. 2020 Apr 1;30(7):126987. doi: 10.1016/j.bmcl.2020.126987. Epub 2020 Jan 27.

Abstract

Pyrrolobenzodiazepines (PBDs) and their dimers (bis-PBDs) have emerged as some of the most potent chemotherapeutic compounds and are currently under development as novel payloads in antibody-drug conjugates (ADCs). However, when used as stand-alone therapeutics or as warheads for small molecule drug conjugates (SMDCs), dose-limiting toxicities are often observed. As an elegant solution to this inherent problem, we designed and synthesized a diazepine-ring-opened bis-PBD prodrug (pro-PBD-PBD) folate conjugate lacking the one of the two imine moieties found in the corresponding free bis-PBD. Upon entering a targeted cell, cleavage of the linker system, including the hydrolysis of an oxazolidine moiety, results in the formation of a reactive intermediate which possesses a newly formed aldehyde as well as an aromatic amine. A fast and spontaneous intramolecular ring-closing reaction subsequently takes place as the aromatic amine adds to the aldehyde with the loss of water to give the imine, and as a result, the diazepine ring, thereby delivering the bis-PBD to the targeted cell. The in vitro and in vivo activity of this conjugate has been evaluated on folate receptor positive KB cells. Sub-nanomolar activity with good specificity and high cure rates with minimal toxicity have been observed.

Keywords: Conjugate; Folate-receptor; Prodrug; Pyrrolobenzodiazepine; Targeted therapy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Antibiotics, Antineoplastic / chemical synthesis
  • Antibiotics, Antineoplastic / pharmacology
  • Antibiotics, Antineoplastic / therapeutic use*
  • Benzodiazepines / chemical synthesis
  • Benzodiazepines / pharmacology
  • Benzodiazepines / therapeutic use*
  • Drug Design
  • Female
  • Folate Receptors, GPI-Anchored / metabolism*
  • HeLa Cells
  • Humans
  • Mice, Nude
  • Neoplasms / drug therapy*
  • Prodrugs / chemical synthesis
  • Prodrugs / pharmacology
  • Prodrugs / therapeutic use*
  • Pyrroles / chemical synthesis
  • Pyrroles / pharmacology
  • Pyrroles / therapeutic use*
  • Xenograft Model Antitumor Assays

Substances

  • Antibiotics, Antineoplastic
  • Folate Receptors, GPI-Anchored
  • Prodrugs
  • Pyrroles
  • Benzodiazepines