Density Functional Theory Study of the Mechanisms of Iron-Catalyzed Aminohydroxylation Reactions

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• 作者：Qinghua Ren ; Shuhui Guan ; Xiaoyan Shen ; Jianhui Fang
• 刊名：Organometallics
• 出版年：2014
• 出版时间：March 24, 2014
• 年：2014
• 卷：33
• 期：6
• 页码：1423-1430
• 全文大小：528K
• 年卷期：v.33,no.6(March 24, 2014)
• ISSN：1520-6041

文摘

Experimental studies recently show that iron salts are effective catalysts for oxaziridine-mediated oxyamination reactions, in place of the powerful osmium-catalyzed Sharpless aminohydroxylation method. The present study reports a theoretical analysis of the mechanism of the iron-catalyzed aminohydroxylation reaction between vinylbenzene and N-sulfonyloxaziridine substrate using density functional theory (DFT) calculations. Our calculations show that the Fe(II)-catalyzed process is favored over the Fe(III)-catalyzed process for the overall catalytic cycle. The rate-limiting step in the whole catalytic cycle is the process of forming the final aminohydroxylation product from a six-membered-ring intermediate, but the solvation effect in MeCN of this step leads to a lowering of the energy barrier computed using the C-PCM method. The regioselectivity has also been investigated.