New Strategy for Synthesis of Bis-Pocket Metalloporphyrins Enabling Regioselective Catalytic Oxidation of Alkanes
New Strategy for Synthesis of Bis-Pocket Metalloporphyrins Enabling Regioselective Catalytic Oxidation of Alkanes
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DOI：
10.1246/bcsj.20210236
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发表时间：
2021-10-01
影响因子：
4
通讯作者：
Higuchi, Tsunehiko
中科院分区：
文献类型：
--
作者：
Amano, Taisei;Inagaki, Hideki;Higuchi, Tsunehiko
细胞色素P450选择性羟基化脂肪酸的ω和ω-1位置。在合成的氧化催化剂中，Suslick的双口袋卟啉Mn或Fe络合物实现。首次进行了氧化反应，但由于空间位阻的原因，催化剂制备中的产率很差，此外，氧化反应中的催化剂周转数也很低。我们设计了一种新的合成策略，包括在构建卟啉骨架后，在meso-苯基的2，6-位引入8个大体积芳基。这一策略大大提高了催化剂的合成产率，并制备了一系列双口袋卟啉衍生物及其金属配合物。这些钌配合物显示出独特的ω-1选择性，并提供了一个更高的转换数在线性烷烃的氧化与2，6-二氯吡啶N-氧化物，相比，由传统的钌卟啉催化的反应。
Cytochrome P450 selectively hydroxylates the omega and omega-1 positions of fatty acids. Among synthetic oxidizing catalysts, Suslick's bis-pocket porphyrin Mn or Fe complex achieved. oxidation for the first time, but the yield in the preparation of the catalyst was poor due to steric hindrance, and in addition, the catalyst turnover number in the oxidation reaction was low. We have devised a new synthetic strategy involving the introduction of eight bulky aryl groups at the 2,6-positions of the meso-phenyl groups after construction of the porphyrin skeleton. This strategy greatly improved the yield in synthesis of the catalyst, and a number of derivatives of bis-pocket porphyrin and their metal complexes were prepared. These Ru complexes show unique omega-1 selectivity and provide a much higher turnover number in the oxidation of linear alkane with 2,6-dichloropyridine N-oxide, as compared to the reaction catalyzed by conventional Ru porphyrins.