Mechanistic Insights on the Iodine(III)-Mediated α-Oxidation of Ketones
Mechanistic Insights on the Iodine(III)-Mediated α-Oxidation of Ketones
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DOI：
10.1002/chem.201501177
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发表时间：
2015-07-27
影响因子：
4.3
通讯作者：
Legault, Claude Y.
中科院分区：
文献类型：
--
作者：
Beaulieu, Samuel;Legault, Claude Y.
α-取代的羰基化合物的合成非常重要，因为它们普遍存在于天然和人造的生物活性化合物中。高价碘化学领域为获取这些分子做出了巨大贡献。例如，羰基化合物的α-氧化是研究最多的碘(III)介导的立体选择性转化之一。然而，在实现高立体选择性方面，这种转变也遇到了最大的挑战。已经研究了碘（III）介导的酮的α-甲苯磺酰氧基化的不同机制途径。计算结果表明，碘 (III) 促进了前所未有的烯醇化过程。据报道，碘鎓中间体可以作为高效的路易斯酸。这一概念可能会产生广泛的影响并促进高价碘化学领域的新发展。
The synthesis of alpha-substituted carbonyl compounds is of great importance due to their ubiquity in both natural and man-made biologically active compounds. The field of hypervalent iodine chemistry has been a great contributor to access these molecules. For example, the alpha-oxidation of carbonyl compounds has been one of the most investigated iodine(III)-mediated stereoselective transformations. Yet, it is also the transformation that has met the most challenge in terms of achieving high stereoselectivities. The different mechanistic pathways of the iodine(III)-mediated alpha-tosyloxylation of ketones have been investigated. The calculations suggest an unprecedented iodine(III)-promoted enolization process. Indications that iodonium intermediates could serve as proficient Lewis acids are reported. This concept could have broad impact and foster new developments in the field of hypervalent iodine chemistry.