Selective Cyclooxygenase Inhibitors: Novel 1,2-Diarylcyclopentenes Are Potent and Orally Active COX-2 Inhibitors

Journal of Medicinal Chemistry
1994.0

Abstract

Our interest in this area has been to develop novel selective inhibitors of cyclooxygenase that have improved therapeutic properties relative to currently used NSAIDs. Toward that goal, we investigated a series of 1,2-diaryl-substituted cyclopentenes based on the hypothesis that the heterocyclic ring in DuP 697 and SC-58125 primarily provides necessary double bond geometry and could be replaced by a carbocycle (cyclopentene). 1-[2-(4-Fluorophenyl)cyclopenten-1-yl]-4-[methylsulfonyl]benzene (la) was synthesized from commercially available 1,2-dibromocyclopentene via three steps (Scheme 1). La was a very potent COX-2 inhibitor (IC50 = 0.026 μM) with essentially no COX-1 activity (IC50 > 100 μM, selectivity > 3800). A structure-activity relationship (SAR) study varying substituents on the 4-fluorophenyl ring of la showed replacing fluorine with chlorine (Ic) or methyl (Id) increased COX-2 potency (IC50 = 0.003 μM) and selectivity (> 33,000), while removing the substituent (le) reduced potency by almost two orders of magnitude. A second SAR study on geminal substitution at the 4-position of the cyclopentene ring (Table 2) revealed analogs generally had reduced selectivity due to increased COX-1 activity and were highly sensitive to steric bulk (e.g., replacing methyl with ethyl in 7a vs 7d led to over 3 orders of magnitude loss in COX-2 activity). In vivo testing showed la was orally active in the rat adjuvant-induced arthritis model (ED50 = 1.7 mpk), and no gastric lesions were observed in mice at 600 mpk or intestinal damage in rats at 200 mpk. In summary, novel 1,2-diarylcyclopentenes are very potent COX-2 inhibitors with IC50 in the low nanomolar range and enzyme selectivity ratios as high as 4 orders of magnitude, orally active in arthritis models with minimal gastrointestinal toxicity.

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