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1,4‐Dehydrogenation with a Two‐Coordinate Cyclic (Alkyl)(amino)silylene
Author(s) -
Koike Taichi,
Kosai Tomoyuki,
Iwamoto Takeaki
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901407
Subject(s) - dehydrogenation , silylene , chemistry , alkyl , hydrogen atom abstraction , reagent , yield (engineering) , medicinal chemistry , photochemistry , organic chemistry , hydrogen , catalysis , materials science , silicon , metallurgy
Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4‐dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4‐dehydrogenation reagent for organic compounds. For the reaction with 9,10‐dimethyl‐9,10‐dihydroanthracene, silylene 1 activated not only benzylic C−H bonds but also aromatic C−H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10‐dihydroanthracene and 1,4‐cyclohexadiene are consistent with the notion that 1,4‐dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen‐abstraction mechanism.