Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation.
Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation.
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DOI：
10.1038/nchem.2835
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发表时间：
2017-12
期刊：
影响因子：
21.8
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Hill CK;Hartwig JF
带有一个或多个羟基的多氧烃包括大量天然和合成化合物，通常具有有效的生物活性。在合成化学中，醇是羰基的重要前体，然后可以转化为广泛的氧或氮基官能团。因此，将天然产物中的单个羟基选择性转化为酮将使得能够选择性引入非天然官能团。然而，已知的转化简单醇或甚至含有多个受保护官能团的分子中的醇的方法不适合于复杂多元醇结构的选择性反应。我们提出了一种新的钌催化剂，具有独特的功效，选择性氧化的一个单一的羟基基团之间的许多未保护的多元醇天然产物。这种氧化能够将氮基官能团引入到缺乏氮原子的结构中，并能够通过逐步或可逆的氧化和还原进行选择性醇差向异构化。
Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.
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影响因子：
5.2
作者：
Kwon, MS;Kim, N;Park, J
通讯作者：
Park, J
影响因子：
--
作者：
Arnone, Alberto;Bava, Adriana;Fontana, Gabriele
通讯作者：
Fontana, Gabriele
影响因子：
2.1
作者：
Scott, Robert W.;Murphy, Annabel C.;Willis, Christine L.
通讯作者：
Willis, Christine L.
影响因子：
15
作者：
Chung, Kevin;Banik, Steven M.;Waymouth, Robert M.
通讯作者：
Waymouth, Robert M.
影响因子：
5.2
作者：
Kim, Won-Hee;Park, In Soo;Park, Jaiwook
通讯作者：
Park, Jaiwook