Khanna I K, Weier R M, Yu Y, Collins P W, Miyashiro J M, Koboldt C M, Veenhuizen A W, Currie J L, Seibert K, Isakson P C
Searle Research and Development, Skokie, Illinois 60077, USA.
J Med Chem. 1997 May 23;40(11):1619-33. doi: 10.1021/jm970036a.
Series of 1,2-diarylpyrroles has been synthesized and found to contain very potent and selective inhibitors of the human cyclooxygenase-2 (COX-2) enzyme. The paper describes short and practical syntheses of the target molecules utilizing the Paal-Knorr reaction. Electrophilic substitution on 1 proceeds in a regioselective fashion, and the method was used to generate a number of tetrasubstituted pyrroles. Detailed SAR on the series has been studied by modifications of the aryl rings and the substituents in the pyrrole ring. Diarylpyrrole 1 is a very potent (COX-2, IC50 = 60 nm) and selective (COX-1/COX-2 = > 1700) inhibitor whereas the isomeric 2 is completely inactive against COX-2. Modifications of the substituents on the fluorophenyl ring in 1 yields very potent inhibitors of COX-2 (IC50 = 40-80 nm) with excellent selectivity (1200 to > 2500) vs COX-1. Analog 20 containing a sulfonamide group is an excellent inhibitor of COX-2 with an IC50 of 14 nm. Tetrasubstituted pyrroles containing groups such as COCF3, SO2CF3, or CH2OAr at position 3 in the pyrrole ring give excellent inhibitors (COX-2, IC50 = 30-120 nm). In vivo testing in the carrageenan-induced paw edema model in the rat establishes that the 1,2-diarylpyrroles are orally active antiinflammatory agents. Compound 3 is the most potent inhibitor of edema with an ED50 of 4.7 mpk.
已合成了一系列1,2 - 二芳基吡咯,并发现其中含有对人环氧化酶 - 2(COX - 2)具有非常强效和选择性抑制作用的化合物。该论文描述了利用帕尔 - 克诺尔反应对目标分子进行的简短且实用的合成方法。1上的亲电取代反应具有区域选择性,该方法用于生成多种四取代吡咯。通过对芳基环和吡咯环上的取代基进行修饰,对该系列化合物进行了详细的构效关系研究。二芳基吡咯1是一种非常强效的(COX - 2,IC50 = 60 nM)且具有选择性的(COX - 1/COX - 2 = > 1700)抑制剂,而异构体2对COX - 2完全无活性。对1中氟苯环上的取代基进行修饰,得到了对COX - 2具有非常强效抑制作用的化合物(IC50 = 40 - 80 nM)以及相对于COX - 1具有优异选择性(1200至> 2500)的化合物。含有磺酰胺基团的类似物20是一种优异的COX - 2抑制剂,IC50为14 nM。在吡咯环3位含有诸如COCF3、SO2CF3或CH2OAr等基团的四取代吡咯可得到优异的抑制剂(COX - 2,IC50 = 30 - 120 nM)。在大鼠角叉菜胶诱导的爪肿胀模型中的体内试验表明,1,2 - 二芳基吡咯是口服活性抗炎剂。化合物3是最有效的水肿抑制剂,ED50为4.7 mpk。