Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions.
Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions.
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DOI：
10.1002/anie.201507180
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发表时间：
2016-01-04
期刊：
影响因子：
--
通讯作者：
Muñiz K
中科院分区：
文献类型：
--
作者：
Haubenreisser S;Wöste TH;Martínez C;Ishihara K;Muñiz K
迄今为止，最著名的手性非外消旋高价碘 (III) 试剂的分子结构首次得到阐明。基于选择性氢键排列的手性诱导超分子支架的形成为这些试剂的持续高不对称诱导提供了解释。作为一个探索性的例子，它们作为手性催化剂的范围扩展到烯烃的对映选择性双氧化。一系列末端苯乙烯在温和条件下转化为相应的邻位双乙酰氧基化产物，并为碘（I/III）催化下真正的分子间不对称烯烃氧化提供了原理证明。
Molecular structures of the most prominent chiral non‐racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen‐bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis.