Selective 1,2-Aminoisothiocyanation of 1,3-Dienes Under Visible-Light Photoredox Catalysis
Selective 1,2-Aminoisothiocyanation of 1,3-Dienes Under Visible-Light Photoredox Catalysis
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DOI：
10.1002/anie.202014518
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发表时间：
2020-12-23
影响因子：
16.6
通讯作者：
Zhu, Jieping
中科院分区：
文献类型：
--
作者：
Guo, Weisi;Wang, Qian;Zhu, Jieping
1，3-二烯的选择性三组分1，2-二氨基化，同时引入两个正交保护的氨基，尽管它有很大的合成潜力，但仍然未知。本文报道了在温和的光氧化还原条件下，共轭双烯与N-氨基吡啶盐反应生成1，2-氨基异硫氰化产物，具有较高的化学选择性和区域选择性。机理研究表明，在光催化条件下，烯丙基硫氰酸酯容易异构化为烯丙基异硫氰酸酯，这是导致观察到的产物选择性形成的原因。温和的异构化反应有望在异硫氰酸烯丙酯的合成中得到广泛的应用。
Selective three-component 1,2-diamination of 1,3-dienes with concurrent introduction of two orthogonally protected amino groups remains unknown despite its significant synthetic potential. We report herein that reaction of conjugated dienes with N-aminopyridinium salts and TMSNCS affords 1,2-aminoisothiocyanation products in a highly chemo- and regio-selective manner under mild photoredox catalytic conditions. Mechanistic studies indicate that the facile isomerization of allyl thiocyanates to allyl isothiocyanates under photocatalytic conditions is responsible for the selective formation of the observed products. The mild isomerization protocol is expected to find applications in the synthesis of allyl isothiocyanates in a broad sense.