Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
College of Chemistry & Molecular Engineering, Qingdao University of Science & Technology, 53 Zhengzhou Road, Qingdao, P. R. China.
Angew Chem Int Ed Engl. 2021 Feb 19;60(8):4085-4089. doi: 10.1002/anie.202014518. Epub 2020 Dec 23.
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.
尽管具有重要的合成潜力，但选择性地将两个正交保护的氨基基团同时引入 1,3-二烯的 1,2-二氨基化反应仍然未知。本文报道了在温和的光氧化还原催化条件下，共轭二烯与 N-氨吡啶盐和 TMSNCS 的反应以高化学和区域选择性方式得到 1,2-氨基异硫氰酸酯产物。机理研究表明，在光催化条件下，烯丙基硫氰酸酯的易于异构化为烯丙基异硫氰酸酯是导致观察到的产物选择性形成的原因。温和的异构化方案有望在广泛意义上用于合成烯丙基异硫氰酸酯。
