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Photoinduced metal‐free hydrocarboxylation of allylamines
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2024-12-13 , DOI: 10.1002/adsc.202401326 Dominika Kobus-Bartoszewicz, Mariusz Zalewski, Krzysztof Melcer, Mikołaj Warda, Sebastian Stecko
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2024-12-13 , DOI: 10.1002/adsc.202401326 Dominika Kobus-Bartoszewicz, Mariusz Zalewski, Krzysztof Melcer, Mikołaj Warda, Sebastian Stecko
Herein, we disclose a new photochemical process to prepare γ‐amino acids from allylamines and formic acid salts. The investigated redox‐neutral hydrocarboxylation process produces high yields across a wide range of functionalized allylamine substrates with excellent regioselectivity. The developed operationally simple protocol can be readily scaled with low photocatalyst loading (from 1% up to 0.02 mol%) without the need for any precautions to exclude air or moisture. The mechanistic working model utilizes a thiol‐catalyzed radical chain process, delivering the hydrogen atom and CO2 from formic acid salt across the alkene substrate through the carboxylate radical (CO2•‐), a crucial reactive intermediate.
中文翻译:
烯丙胺的光诱导无金属氢羧化
在此,我们公开了一种从烯丙胺和甲酸盐制备γ-氨基酸的新光化学工艺。所研究的氧化还原-中性氢羧化工艺可在多种官能化烯丙胺底物上产生高产率,并具有优异的区域选择性。开发的操作简单的方案可以在低光催化剂负载量(从 1% 到 0.02 mol%)下轻松缩放,而无需采取任何预防措施来排除空气或水分。机理工作模型利用巯基催化的自由基链过程,通过羧酸盐自由基 (CO2•‐) 将氢原子和 CO2 从甲酸盐盐输送到烯烃底物上,这是一种重要的反应性中间体。
更新日期:2024-12-13
中文翻译:
烯丙胺的光诱导无金属氢羧化
在此,我们公开了一种从烯丙胺和甲酸盐制备γ-氨基酸的新光化学工艺。所研究的氧化还原-中性氢羧化工艺可在多种官能化烯丙胺底物上产生高产率,并具有优异的区域选择性。开发的操作简单的方案可以在低光催化剂负载量(从 1% 到 0.02 mol%)下轻松缩放,而无需采取任何预防措施来排除空气或水分。机理工作模型利用巯基催化的自由基链过程,通过羧酸盐自由基 (CO2•‐) 将氢原子和 CO2 从甲酸盐盐输送到烯烃底物上,这是一种重要的反应性中间体。