金属卟啉丙烯酸酯的合成及其在不同氧源下催化环己烷羟化的研究

Synthesis and catalytic activities in cyclohexane hydroxylation of metalloporphyrin acrylates using different monooxygenase resource

目的寻找金属卟啉类催化羟化环己烷的优良催化剂及催化条件。方法合成了一系列带不同取代基的锰(钴)卟啉丙烯酸酯,研究了它们在以分子氧或亚碘酰苯做氧源时对环己烷的催化羟化情况,并对催化效果进行了理论分析。结果成功合成了金属卟啉丙烯酸酯系列化合物;在以分子氧为氧源时,具有推电子取代基的卟啉比具有吸电子取代基的催化效果更好,而以亚碘酰苯为氧源时情况恰好相反;不论以分子氧还是亚碘酰苯为氧源,锰卟啉都要比对应的钴卟啉具有更高的催化活性。结论锰卟啉丙烯酸酯是潜在的羟化环己烷的优良催化剂。

Objective Mn（Ⅲ） and Co（Ⅱ） porphyrin acrylates were synthesized in order to get optimal cyclohexane hydroxylation catalysts and catalytic conditions.Methods Mn（Ⅲ） and Co（Ⅱ） porphyrin acrylates appending different peripheral substituents were synthesized and their catalytic activities in the cyclohexane hydroxylation with O2 or PhIO were investigated comparatively by using theoretic analysis.Results The metalloporphyrins with electron-donating groups as subtituents had much higher catalytic efficiencies than those with electron-withdrawing groups when O2 was used as monooxygenase resource,while the result turned to be the contrary when the monooxygenase resource was replaced by PhIO.However,the Mn（Ⅲ） porphyrins always showed higher catalytic efficiency than Co（Ⅱ） porphyrins using either O2 or PhIO as monooxygenase resource because of the larger contribution of d electrons to the LUMO-HOMO levels of the isolated metalloporphyrin.Conclusion Mn（Ⅲ） porphyrin acrylates are potential cyclohexane hydroxylation catalysts which show high catalytic efficiency.