Iron-Catalyzed Direct Diazidation for a Broad Range of Olefins.
Iron-Catalyzed Direct Diazidation for a Broad Range of Olefins.
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DOI：
10.1002/anie.201507550
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发表时间：
2016-01-11
期刊：
影响因子：
--
通讯作者：
Xu H
中科院分区：
文献类型：
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作者：
Yuan YA;Lu DF;Chen YR;Xu H
本文报道了一种新的铁催化的非对映选择性烯烃二叠氮化反应，其在室温下发生（1 - 5摩尔%的催化剂和d.r.最大值> 20：1）。该方法容许宽范围的未官能化和高度官能化的烯烃，包括与现有方法不相容的那些。它还提供了一种方便的方法，以邻位伯二胺以及其他合成有价值的含氮结构单元，这是难以获得的替代方法。初步的机理研究表明，该反应可能通过一个新的机理途径进行，其中刘易斯酸活化和铁激活的氧化还原催化是至关重要的选择性叠氮基转移。
Reported herein is a new iron-catalyzed diastereo-selective olefin diazidation reaction which occurs at room temperature (1–5 mol % of catalysts and d.r. values of up to > 20:1). This method tolerates a broad range of both unfunctionalized and highly functionalized olefins, including those that are incompatible with existing methods. It also provides a convenient approach to vicinal primary diamines as well as other synthetically valuable nitrogen-containing building blocks which are difficult to obtain with alternative methods. Preliminary mechanistic studies suggest that the reaction may proceed through a new mechanistic pathway in which both Lewis acid activation and iron-enabled redox-catalysis are crucial for selective azido-group transfer.