Jacobson K A, Kim Y C, King B F
Molecular Recognition Section, Bldg. 8A, Rm. B1A-19, Laboratory of Bioorganic Chemistry, National Institute of Diabetes and Digestive and Kidney Diseases, NIH, Bethesda, MD 20892-0810, USA.
J Auton Nerv Syst. 2000 Jul 3;81(1-3):152-7. doi: 10.1016/s0165-1838(00)00128-4.
1,4-Dihydropyridines are regarded as privileged structures for drug design, i.e. they tend to bind to a wide variety of receptor sites. We have shown that upon appropriate manipulation of the substituent groups on a 1,4-dihydropyridine template, high affinity and selectivity for the A(3) subtype of adenosine receptors ('P1 receptors') may be attained. In the present study we have begun to extend this approach to P2 receptors which are activated by ATP and other nucleotides. Nicardipine, a representative dihydropyridine, used otherwise as an L-type calcium channel blocker, was shown to be an antagonist at recombinant rat P2X(2) (IC(50)=25 microM) and P2X(4) (IC(50) approximately 220 microM) receptors expressed in Xenopus oocytes. Thus, this class of compounds represents a suitable lead for enhancement of affinity through chemical synthesis. In an attempt to modify the 1,4-dihydropyridine structure with a predicted P2 receptor recognition moiety, we have replaced one of the ester groups with a negatively charged phosphonate group. Several 4-phenyl-5-phosphonato-1,4-dihydropyridine derivatives, MRS 2154 (2, 6-dimethyl), MRS 2155 (6-methyl-2-phenyl), and MRS 2156 (2-methyl-6-phenyl), were synthesized through three component condensation reactions. These derivatives were not pure antagonists of the effects of ATP at P2X(2) receptors, rather were either inactive (MRS 2156) or potentiated the effects of ATP in a concentration-dependent manner (MRS 2154 in the 0.3-10 microM range and MRS 2155 at >1 microM). Antagonism of the effects of ATP at P2X(2) receptor superimposed on the potentiation was also observed at >10 microM (MRS 2154) or 0.3-1 microM (MRS 2155). Thus, while a conventional dihydropyridine, nicardipine, was found to antagonize rat P2X(2) receptors ninefold more potently than P2X(4) receptors, the effects of novel, anionic 5-phosphonate analogues at the receptor were more complex.
1,4 - 二氢吡啶被视为药物设计中的优势结构,即它们倾向于与多种受体位点结合。我们已经表明,对1,4 - 二氢吡啶模板上的取代基进行适当操作后,可实现对腺苷受体(“P1受体”)A(3)亚型的高亲和力和选择性。在本研究中,我们已开始将此方法扩展至由ATP和其他核苷酸激活的P2受体。硝苯地平是一种代表性的二氢吡啶,在其他方面用作L型钙通道阻滞剂,结果显示它是非洲爪蟾卵母细胞中表达的重组大鼠P2X(2)受体(IC(50)=25 microM)和P2X(4)受体(IC(50)约为220 microM)的拮抗剂。因此,这类化合物是通过化学合成提高亲和力的合适先导物。为了用预测的P2受体识别基团修饰1,4 - 二氢吡啶结构,我们用带负电荷的膦酸酯基团取代了其中一个酯基。通过三组分缩合反应合成了几种4 - 苯基 - 5 - 膦酸酯基 - 1,4 - 二氢吡啶衍生物,MRS 2154(2,6 - 二甲基)、MRS 2155(6 - 甲基 - 2 - 苯基)和MRS 2156(2 - 甲基 - 6 - 苯基)。这些衍生物并非ATP对P2X(2)受体作用的纯粹拮抗剂,而是要么无活性(MRS 2156),要么以浓度依赖方式增强ATP的作用(MRS 2154在0.3 - 10 microM范围内,MRS 2155在>1 microM时)。在>10 microM(MRS 2154)或0.3 - 1 microM(MRS 2155)时,还观察到在增强作用之上叠加的ATP对P2X(2)受体作用的拮抗作用。因此,虽然发现传统的二氢吡啶硝苯地平对大鼠P2X(2)受体的拮抗作用比对P2X(4)受体强九倍,但新型阴离子5 - 膦酸酯类似物对该受体的作用更为复杂。