Phosphinylation of Non-activated Aryl Fluorides through Nucleophilic Aromatic Substitution at the Boundary of Concerted and Stepwise Mechanisms
Zhensheng You
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorDr. Kosuke Higashida
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, 001-0021 Japan
Search for more papers by this authorCorresponding Author
Dr. Tomohiro Iwai
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Masaya Sawamura
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, 001-0021 Japan
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorZhensheng You
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorDr. Kosuke Higashida
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, 001-0021 Japan
Search for more papers by this authorCorresponding Author
Dr. Tomohiro Iwai
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Masaya Sawamura
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, 001-0021 Japan
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorAbstract
Non-activated aryl fluorides reacted with potassium diorganophosphinites through a nucleophilic aromatic substitution (SNAr) reaction. Remarkably, both electron-neutral and electron-rich aryl fluorides participated in the reaction with substantially stabilized anionic P nucleophiles to form the corresponding tertiary phosphine oxides. Quantum chemical calculations suggested a nucleophile-dependent mechanism that involves both concerted and stepwise SNAr reaction pathways.
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