Lowbridge J, Manning M, Haldar J, Sawyer W H
J Med Chem. 1977 Jan;20(1):120-3. doi: 10.1021/jm00211a025.
[4-Threonine, 7-glycine]oxytocin and [1-(L-2-hydroxy-3-mercaptopropanoic acid), 4-threonine, 7-glycine]oxytocin (hydroxy[Thr4, Gly7]oxytocin) were synthesized by a combination of solid-phase and classical methods of peptide synthesis. A protected octapeptide was synthesized by the solid-phase method and following ammonolysis and purification 1 + 8 couplings in solution were employed to furnish the required key nonapeptide and acyl octapeptide intermediates, respectively. [7-Glycine]oxytocin was prepared from a sample of the protected nonapeptide intermediate used in the original synthesis of this peptide. [7-Glycine]oxytocin has an oxytocic potency (O) of 93 +/- 4 units/mg and an antidiuretic potency (A) of 0.0056 +/- 0.0003 units/mg. It has an O/A ratio of 16 000. [4-Threonine, 7-glycine]oxytocin has an oxytocic potency of 166 +/- 4 units/mg and an antidiuretic potency of 0.002 +/- 0.0004 units/mg. Its O/A ratio is 83 000. Threonine substitution has thus brought about a substantial enhancement in oxytocic activity and a fivefold enhancement in O/A selectivity. Hydroxy [Thr4, Gly7]oxytocin has an oxytocic potency of 218 +/- 8 units/mg and antidiuretic potency of 0.0040 +/- 0.0005 units/mg. Its O/A ratio is thus 54 500. All three 7-glycine-substituted analogues exhibit a marked sensitivity to Mg2+ on the rat uterus assay ststem and in the presence of 0.5 mM Mg2+ had oxytocic potencies in the range of 900-1000 units/mg. Should these peptides exhibit enhanced oxytocic selectivity in humans, they might offer a greater margin of safety than oxytocin in those clinical stiuations in which the latter is currently employed.
[4-苏氨酸,7-甘氨酸]缩宫素和[1-(L-2-羟基-3-巯基丙酸),4-苏氨酸,7-甘氨酸]缩宫素(羟基[苏氨酸4,甘氨酸7]缩宫素)通过固相法和经典肽合成方法相结合合成。通过固相法合成了一个受保护的八肽,在氨解和纯化后,分别采用溶液中的1 + 8偶联反应来提供所需的关键九肽和酰基八肽中间体。[7-甘氨酸]缩宫素由该肽最初合成中使用的受保护九肽中间体样品制备。[7-甘氨酸]缩宫素的催产效力(O)为93±4单位/毫克,抗利尿效力(A)为0.0056±0.0003单位/毫克。其O/A比值为16000。[4-苏氨酸,7-甘氨酸]缩宫素的催产效力为166±4单位/毫克,抗利尿效力为0.002±0.0004单位/毫克。其O/A比值为83000。因此,苏氨酸取代使催产活性显著增强,O/A选择性提高了五倍。羟基[苏氨酸4,甘氨酸7]缩宫素的催产效力为218±8单位/毫克,抗利尿效力为0.0040±0.0005单位/毫克。其O/A比值因此为54500。所有三种7-甘氨酸取代的类似物在大鼠子宫测定系统中对Mg2+表现出明显的敏感性,在存在0.5 mM Mg2+的情况下,催产效力在900 - 1000单位/毫克范围内。如果这些肽在人类中表现出增强的催产选择性,那么在目前使用缩宫素的那些临床情况下,它们可能比缩宫素提供更大的安全边际。