Tetrahydroquinoline units in flexible heteroarotinoids (Flex-Hets) convey anti-cancer properties in A2780 ovarian cancer cells

  • Krishna Kumar Gnanasekaran
  • , Tim Pouland
  • , Richard A. Bunce
  • , K. Darrell Berlin
  • , Suaad Abuskhuna
  • , Dipendra Bhandari
  • , Maryam Mashayekhi
  • , Donghua H. Zhou
  • , Doris M. Benbrook

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

SHetA2 (NSC 721689), our lead Flex-Het anti-cancer agent, consists of a thiochroman (Ring A) and a 4-nitrophenyl (Ring B) linked by a thiourea bridge. In this work, several series of new analogs having a tetrahydroquinoline (THQ, Ring A) unit connected by a urea or thiourea linker to a 4-substituted phenyl (Ring B) have been prepared and evaluated relative to SHetA2 in terms of binding affinity with mortalin and inhibition of A2780 ovarian cancer cells. Six of the derivatives equaled or exceeded the efficacy shown by SHetA2. Compounds 1a-d (series 1), lacking a methyl on the Ring A nitrogen and the gem-dimethyls on the adjacent carbon, showed only weak activity. Salt 2, the quaternized N,N-dimethyl iodide salt analog of 1a, also possessed very modest growth inhibition in the cell line studied. Series 3 compounds, which had a C3 ketone and an N-methyl replacing the sulfur in Ring A, were most successful. Compound 3a [Ring A = 1,2,2,4,4-pentamethyl-3-oxo-1,2,3,4-tetrahydroquinolin-6-yl; urea linker; Ring B = 4-nitrophenyl] had slightly lower potency (IC50 3.8 μM), but better efficacy (94.8%) than SHetA2 (IC50 3.17 μM, efficacy 84.3%). In addition, 3c and 3d [urea and thiourea linkers, respectively; Ring B = 4-(trifluoromethyl)phenyl] and 3e and 3f [urea and thiourea linkers, respectively; Ring B = 4-(trifluoromethoxy)phenyl] were also evaluated since these agents possessed electron-withdrawing groups with H-bonding capability. All displayed good activity. Compounds 3c and 3e showed improvement in both potency and efficacy compared to SHetA2. In general, when the linker group between Rings A and B was a urea, efficacy values slightly exceeded those with a thiourea linker in the carbonyl-containing THQ systems 3a-g. In contrast, when Ring A possessed the 1,2,2,4,4-pentamethyl-3-hydroxytetrahydroquinolin-6-yl unit (4a-f, series 4), very modest potency and efficacy was observed. Model compound 5, an exact N-methyl THQ analog of SHetA2, demonstrated less potency (IC50 4.5 μM), but improved efficacy (91.7%). Modeling studies were performed to rationalize the observed results.

Original languageEnglish
Article number115244
JournalBioorganic and Medicinal Chemistry
Volume28
Issue number1
DOIs
StatePublished - Jan 1 2020
Externally publishedYes

Funding

The investigators (KDB, RAB and DHZ) gratefully acknowledge support of this research by the Stephenson Cancer Research Center/Oklahoma Tobacco Settlement Endowment Trust (TSET). The authors also wish to thank OSU for a President's Fellows Faculty Research Award to DHZ. The authors are grateful to the OSU College of Arts and Sciences for funds that allowed the Chemistry Department to purchase a new A-400 MHz NMR unit for our State-Wide NMR facility. The State-Wide NMR facility was originally established with support from the NSF (BIR-9512269), the Oklahoma State Regents for Higher Education, the W. M. Keck Foundation, and Conoco, Inc. The investigators (KDB, RAB and DHZ) gratefully acknowledge support of this research by the Stephenson Cancer Research Center/Oklahoma Tobacco Settlement Endowment Trust (TSET) . The authors also wish to thank OSU for a President’s Fellows Faculty Research Award to DHZ. The authors are grateful to the OSU College of Arts and Sciences for funds that allowed the Chemistry Department to purchase a new A-400 MHz NMR unit for our State-Wide NMR facility. The State-Wide NMR facility was originally established with support from the NSF ( BIR-9512269 ), the Oklahoma State Regents for Higher Education , the W. M. Keck Foundation, and Conoco, Inc . Appendix A

Keywords

  • In silico docking study
  • Mortalin
  • SHetA2
  • Structure optimization
  • Tetrahydroquinoline-based anticancer agents

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