Biochemistry/Biophysics Program, Washington State University, 99164-4660, Pullman, Washington, USA.
Photosynth Res. 1986 Jan;8(1):53-63. doi: 10.1007/BF00028476.
The condensation of D-fructose 6-phosphate or 1-phosphate with cyanide has been used to synthesize 2-carboxyhexitol 6-phosphates and 1-phosphates. The products have been characterized in terms of their action on ribulose bisphosphate carboxylase/oxygenase. The reaction of D-fructose 6-phosphate with cyanide is four times as fast (at 22°C) at pH 7.5 than at pH 11.5 and the primary products of condensation are more easily isolated by anion exchange chromatography. Two minor chromatographic peaks (I and II) for diastereomeric 2-carboxyhexitol 6-phosphates are isolated in addition to two major peaks, III and IV, which are lactones. The lactones are those of 2-C-carboxy-D-glucitol 6-phosphate (CG6P) in peak III and 2-C-carboxy-D-mannitol 6-phosphate (CM6P) in peak IV, as established after dephosphorylation by the relative rates of oxidation by periodate and by gas chromatographic retention times of the acetates. Analogous methodology has been used to synthesize the diastereomeric 2-carboxy-hexitol 1-phosphates (CG1P and CM1P) and their lactones from D-fructose 1-phosphate. The four carboxylates inhibit ribulose bisphosphate carboxylase/oxygenase from spinach or Pseudomonas oxalaticus in the following decreasing order of potency: CG6P, CM6P, CG1P, CM1P. The inhibition pattern suggests that the binding of the 5-phosphate moiety of the intermediate in the reaction catalyzed by ribulose bisphosphate carboxylase/oxygenase may be stronger by an order of magnitude than the binding of the 1-phosphate group.
D-果糖 6-磷酸或 1-磷酸与氰化物的缩合已被用于合成 2-羧基己糖 6-磷酸和 1-磷酸。根据它们对核酮糖二磷酸羧化酶/加氧酶的作用，对产物进行了特征描述。在 pH7.5 时，D-果糖 6-磷酸与氰化物的反应速度比在 pH11.5 时快四倍，并且缩合的主要产物更容易通过阴离子交换色谱法分离。除了两个主要峰 III 和 IV（内酯）之外，还分离出两个次要色谱峰 I 和 II，它们是差向立体的 2-羧基己糖 6-磷酸酯。内酯是峰 III 中 2-C-羧基-D-葡萄糖 6-磷酸酯（CG6P）和峰 IV 中 2-C-羧基-D-甘露醇 6-磷酸酯（CM6P）的内酯，如用过碘酸盐氧化的相对速率和乙酸盐的气相色谱保留时间确定的那样。类似的方法已被用于从 D-果糖 1-磷酸合成差向立体的 2-羧基-己糖 1-磷酸酯（CG1P 和 CM1P）及其内酯。这四种羧酸盐按效力递减的顺序抑制来自菠菜或草酸假单胞菌的核酮糖二磷酸羧化酶/加氧酶：CG6P、CM6P、CG1P、CM1P。抑制模式表明，在核酮糖二磷酸羧化酶/加氧酶催化的反应中，中间体的 5-磷酸部分的结合可能比 1-磷酸基团的结合强一个数量级。
