Department of Medicine, University of California, San Francisco, California 94143-0521, United States.
J Med Chem. 2011 Aug 11;54(15):5468-77. doi: 10.1021/jm200505e. Epub 2011 Jul 12.
We previously reported the discovery of pyrimido-pyrrolo-quinoxalinedione (PPQ) inhibitors of the cystic fibrosis transmembrane conductance regulator (CFTR) chloride channel and showed their efficacy in an organ culture model of polycystic kidney disease (PKD) (J. Med. Chem. 2009, 52, 6447-6455). Here, we report related benzopyrimido-pyrrolo-oxazinedione (BPO) CFTR inhibitors. To establish structure-activity relationships and select lead compound(s) with improved potency, metabolic stability, and aqueous solubility compared to the most potent prior compound 8 (PPQ-102, IC(50) ∼ 90 nM), we synthesized 16 PPQ analogues and 11 BPO analogues. The analogues were efficiently synthesized in 5-6 steps and 11-61% overall yield. Modification of 8 by bromine substitution at the 5-position of the furan ring, replacement of the secondary amine with an ether bridge, and carboxylation, gave 6-(5-bromofuran-2-yl)-7,9-dimethyl-8,10-dioxo-11-phenyl-7,8,9,10-tetrahydro-6H-benzo[b]pyrimido [4',5':3,4]pyrrolo [1,2-d][1,4]oxazine-2-carboxylic acid 42 (BPO-27), which fully inhibited CFTR with IC(50) ∼ 8 nM and, compared to 8, had >10-fold greater metabolic stability and much greater polarity/aqueous solubility. In an embryonic kidney culture model of PKD, 42 prevented cyst growth with IC(50) ∼ 100 nM. Benzopyrimido-pyrrolo-oxazinediones such as 42 are potential development candidates for antisecretory therapy of PKD.
我们之前报道了发现吡咯并[2,3-d]嘧啶-4,5-二酮(PPQ)是囊性纤维化跨膜电导调节因子(CFTR)氯离子通道的抑制剂,并在多囊肾病(PKD)的器官培养模型中显示了其疗效(J. Med. Chem. 2009, 52, 6447-6455)。在这里,我们报告了相关的苯并吡咯并[2,3-d]嘧啶-4,5-二酮(BPO)CFTR 抑制剂。为了建立构效关系,并选择与最有效先前化合物 8(PPQ-102,IC50∼90 nM)相比具有更高效力、代谢稳定性和水溶解度的先导化合物,我们合成了 16 个 PPQ 类似物和 11 个 BPO 类似物。类似物通过呋喃环 5 位的溴取代、仲胺用醚桥取代以及羧化,以 5-6 步和 11-61%的总收率进行高效合成。5-溴呋喃-2-基取代 8 位、用醚桥取代仲胺、羧化,得到 6-(5-溴呋喃-2-基)-7,9-二甲基-8,10-二氧代-11-苯基-7,8,9,10-四氢-6H-苯并[b]嘧啶并[4',5':3,4]吡咯[1,2-d][1,4]恶嗪-2-羧酸 42(BPO-27),其完全抑制 CFTR 的 IC50∼8 nM,与 8 相比,代谢稳定性提高了 10 倍以上,极性/水溶性大大提高。在 PKD 的胚胎肾培养模型中,42 以 IC50∼100 nM 阻止了囊肿生长。苯并吡咯并[2,3-d]嘧啶-4,5-二酮类如 42 是 PKD 抗分泌治疗的潜在候选药物。