Esterification of Tertiary Amides: Remarkable Additive Effects of Potassium Alkoxides for Generating Hetero Manganese?Potassium Dinuclear Active Species
Esterification of Tertiary Amides: Remarkable Additive Effects of Potassium Alkoxides for Generating Hetero Manganese?Potassium Dinuclear Active Species
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叔酰胺的酯化反应：醇钾对生成杂锰钾双核活性物质的显着加和作用
DOI：
10.1002/chem.202001447
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Mashima Kazushi
中科院分区：
文献类型：
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作者：
Hirai Takahiro;Kato Daiki;Mai Binh Khanh;Katayama Shoichiro;Akiyama Shoko;Nagae Haruki;Himo Fahmi;Mashima Kazushi
单核锰前体与醇氧钾结合的催化剂体系与我们先前报道的锰单核催化剂相比，不仅可以催化叔芳基酰胺的酯化，还可以催化叔脂肪族酰胺的酯化。基于3和醇酸钾盐的化学计量反应、动力学研究和密度泛函理论（DFT）计算，我们明确了一种合理的反应机制，即原位生成的锰-钾杂双核物质协同激活酰胺的羰基部分和醇的OH部分。我们还详细揭示了我们之前的锰同双核体系2a的反应机理，我们发现锰-钾异双核配合物催化酰胺酯化反应的激活自由能（ΔG≠）低于锰同双核体系，这与实验结果一致。我们进一步应用我们的催化剂体系去保护伯胺和仲胺的乙酰基部分。
A catalyst system of mononuclear manganese precursor3combined with potassium alkoxide served as a superior catalyst compared with our previously reported manganese homodinuclear catalyst2 afor esterification of not only tertiary aryl amides, but also tertiary aliphatic amides. On the basis of stoichiometric reactions of3and potassium alkoxide salt, kinetic studies, and density functional theory (DFT) calculations, we clarified a plausible reaction mechanism in which in situ generated manganese–potassium heterodinuclear species cooperatively activates the carbonyl moiety of the amide and the OH moiety of the alcohols. We also revealed details of the reaction mechanism of our previous manganese homodinuclear system2 a, and we found that the activation free energy (ΔG≠) for the manganese–potassium heterodinuclear complex catalyzed esterification of amides is lower than that for the manganese homodinuclear system, which was consistent with the experimental results. We further applied our catalyst system to deprotect the acetyl moiety of primary and secondary amines.