Monn J A, Valli M J, Massey S M, Wright R A, Salhoff C R, Johnson B G, Howe T, Alt C A, Rhodes G A, Robey R L, Griffey K R, Tizzano J P, Kallman M J, Helton D R, Schoepp D D
Central Nervous System Division, Eli Lilly and Company, Indianapolis, Indiana 46285, USA.
J Med Chem. 1997 Feb 14;40(4):528-37. doi: 10.1021/jm9606756.
2-Aminobicyclo[3.1.0]hexane-2,6-dicarboxylic acid (9) was designed as a conformationally constrained analog of glutamic acid. For 9, the key torsion angles (tau 1 and tau 2) which determine the relative positions of the alpha-amino acid and distal carboxyl functionalities are constrained where tau 1 = 166.9 degrees or 202 degrees and tau 2 = 156 degrees, respectively. We hypothesized that 9 would closely approximate the proposed bioactive conformation of glutamate when acting at group 2 metabotropic glutamate receptors (mGluRs). The racemic target molecule (+/-)-9, its C2-diastereomer (+/-)-16, and its enantiomers (+)-9 (LY354740) and (-)-9 (LY366563) were prepared by an efficient, stereocontrolled, and high-yielding synthesis from 2-cyclopentenone. Our hypothesis that 9 could interact with high affinity and specificity at group 2 mGluRs has been supported by the observation that (+/-)-9 (EC50 = 0.086 +/- 0.025 microM) and its enantiomer (+)-9 (EC50 = 0.055 +/- 0.017 microM) are highly potent agonists for group 2 mGluRs in the rat cerebral cortical slice preparation (suppression of forskolin-stimulated cAMP formation) possessing no activity at other glutamate receptor sites (iGluR or group 1 mGluR) at concentrations up to 100 microM. Importantly, the mGluR agonist effects of (+)-9 are evident following oral administration in mice in both the elevated plus maze model of anxiety (ED50 = 0.5 mg/kg) and in the ACPD-induced limbic seizure model (ED50 = 45.6 mg/kg). Thus, (+)-9 is the first orally active group 2 mGluR agonist described thus far and is an important tool for studying the effects of compounds of this class in humans.
2-氨基双环[3.1.0]己烷-2,6-二羧酸(9)被设计为谷氨酸的构象受限类似物。对于9,决定α-氨基酸和远端羧基官能团相对位置的关键扭转角(τ1和τ2)受到限制,其中τ1 = 166.9°或202°,τ2 = 156°。我们推测,当作用于2型代谢型谷氨酸受体(mGluRs)时,9将紧密接近谷氨酸提出的生物活性构象。通过从2-环戊烯酮进行高效、立体控制且高产率的合成,制备了外消旋目标分子(±)-9、其C2-非对映异构体(±)-16及其对映体(+)-9(LY354740)和(-)-9(LY366563)。我们的假设,即9可以在2型mGluRs上以高亲和力和特异性相互作用,已得到以下观察结果的支持:(±)-9(EC50 = 0.086 ± 0.025 μM)及其对映体(+)-9(EC50 = 0.055 ± 0.017 μM)在大鼠大脑皮层切片制备中是2型mGluRs的高效激动剂(抑制福斯可林刺激的cAMP形成),在浓度高达100 μM时在其他谷氨酸受体位点(离子型谷氨酸受体或1型mGluRs)无活性。重要的是,在焦虑的高架十字迷宫模型(ED50 = 0.5 mg/kg)和ACPD诱导的边缘性癫痫模型(ED50 = 45.6 mg/kg)中,(+)-9经小鼠口服给药后,其mGluR激动剂作用明显。因此,(+)-9是迄今为止描述的首个口服活性2型mGluR激动剂,是研究此类化合物对人类影响的重要工具。