Anwer M K, Porter R A, Spatola A F
Department of Chemistry, University of Louisville, Kentucky.
Int J Pept Protein Res. 1987 Oct;30(4):489-97.
Dehalogenation of chlorine bound to aromatic nuclei has been achieved using ammonium formate-catalytic transfer hydrogenation (AF-CTH) techniques. The use of deuterated ammonium formate as the transfer agent in the CTH process when performed in a deuterated solvent medium results in the predominant formation of the labeled product. Thus, ND+4 DCOO(-)-CTH of [D-Ala2, p-ClPhe4]-Leu-enkephalin in 80% CD3COOD/D2O yielded [D-Ala2, Phe (4D)4]-Leu-enkephalin. Levels of D-incorporation were measured by fast atom bombardment-mass spectrometry (FAB-MS) and/or by 13C n.m.r. spectroscopy. Using D-labeled and unlabeled ammonium formate in stoichiometrically similar reactions, it was concluded that the hydrogenation exhibited a primary kinetic isotope effect. Reactant and product concentrations were determined by amino acid analysis and reversed phase HPLC.
利用甲酸铵催化转移氢化（AF-CTH）技术实现了与芳环结合的氯的脱卤反应。在氘代溶剂介质中进行CTH过程时，使用氘代甲酸铵作为转移剂会导致主要生成标记产物。因此，在80% CD3COOD/D2O中，[D-Ala2, p-ClPhe4]-亮氨酸脑啡肽的ND+4 DCOO(-)-CTH反应生成了[D-Ala2, Phe (4D)4]-亮氨酸脑啡肽。通过快原子轰击质谱（FAB-MS）和/或13C核磁共振光谱法测量氘掺入水平。在化学计量相似的反应中使用氘标记和未标记的甲酸铵，得出氢化反应表现出一级动力学同位素效应的结论。通过氨基酸分析和反相高效液相色谱法测定反应物和产物浓度。
