A Biomimetic Model for the Active Site of [Fe]-H(2)ase Featuring a 2-Methoxy-3,5-dimethyl-4-phosphato-6-acylmethylpyridine Ligand
A Biomimetic Model for the Active Site of [Fe]-H(2)ase Featuring a 2-Methoxy-3,5-dimethyl-4-phosphato-6-acylmethylpyridine Ligand
复制标题
以 2-甲氧基-3,5-二甲基-4-磷酸基-6-酰基甲基吡啶配体为特征的 [Fe]-H(2)ase 活性位点的仿生模型
DOI：
10.1021/acs.organomet.9b00635
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Liu Bei-Bei
中科院分区：
文献类型：
--
作者：
Song Li-Cheng;Zhu Liang;Liu Bei-Bei
在此，我们报道了第一个含有[Fe]-H2ase模型的3,5-二甲基-4-磷酸吡啶部分，[2-MeO-3,5-Me2-4-OP=O(OPh)2-6-COCH2C5N]Fe(CO)2(η2-6-Me-2-SC5H3N) (7)，通过包括七个独立反应步骤的多步合成方法制备。前三个反应步骤用于制备有机前体4-TBSO-3,5,6-三甲基-2-吡啶酮(1)、2-甲氧基-4-TBSO-3,5,6-三甲基吡啶(2)和2-甲氧基-4-TBSO-3,5-二甲基-6-氯甲基吡啶(3)。接下来的三个反应步骤用于制备有机金属前体 (2-MeO-4-TBSO-3,5-Me2-6-COCH2C5N)Fe(CO)3I (4)、(2-MeO-4-TBSO-3,5-Me2-6-COCH2C5N)Fe(CO)2(η2-6-Me-2-SC5H3N) (5) 和(2-MeO-4-HO-3,5-Me2-6-COCH2C5N)Fe(CO)2(η2-6-Me-2-SC5H3N) (6)。最后一步是在 Et3N 存在下，通过 6 与 O=P(OPh)2Cl 的酯化反应来制备目标模型 7。所有制备的有机和有机金属化合物都是新的，并通过元素分析和光谱学以及其中一些通过 X 射线晶体学进行了表征。
Herein, we report the first 3,5-dimethyl-4-phosphatopyridine moiety containing [Fe]-H2ase model, [2-MeO-3,5-Me2-4-OP═O(OPh)2-6-COCH2C5N]Fe(CO)2(η2-6-Me-2-SC5H3N) (7), prepared by a multistep synthetic method including seven separate reaction steps. The first three reaction steps are utilized to prepare the organic precursors 4-TBSO-3,5,6-trimethyl-2-pyridone (1), 2-methoxy-4-TBSO-3,5,6-trimethylpyridine (2), and 2-methoxy-4-TBSO-3,5-dimethyl-6-chloromethylpyridine (3). The next three reaction steps are used to prepare the organometallic precursors (2-MeO-4-TBSO-3,5-Me2-6-COCH2C5N)Fe(CO)3I (4), (2-MeO-4-TBSO-3,5-Me2-6-COCH2C5N)Fe(CO)2(η2-6-Me-2-SC5H3N) (5), and (2-MeO-4-HO-3,5-Me2-6-COCH2C5N)Fe(CO)2(η2-6-Me-2-SC5H3N) (6). The final step is employed to prepare target model7by an esterification reaction of6with O═P(OPh)2Cl in the presence of Et3N. All of the prepared organic and organometallic compounds are new and have been characterized by elemental analysis and spectroscopy and, for some of them, by X-ray crystallography.