化学
光催化
芳基
镍
试剂
氨基甲酸酯
二氧化碳
化学计量学
卤化物
有机化学
无机化学
光化学
催化作用
烷基
作者
Aleksi Sahari,Jukka Puumi,Jere K. Mannisto,Timo Repo
标识
DOI:10.1021/acs.joc.3c00023
摘要
We report the use of dual nickel photocatalysis in the synthesis of O-aryl carbamates from aryl iodides or bromides, amines, and carbon dioxide. The reaction proceeded in visible light, at ambient carbon dioxide pressure, and without stoichiometric activating reagents. Mechanistic analysis is consistent with a Ni(I-III) cycle, where the active species is generated by the photocatalyst. The rate-limiting steps were the photocatalyst-mediated reduction of Ni(II) to Ni(I) and subsequent oxidative addition of the aryl halide. The physical properties of the photocatalyst were critical for promoting formation of O-aryl carbamates over various byproducts. Nine new phthalonitrile photocatalysts were synthesized, which exhibited properties that were vital to achieve high selectivity and activity.
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