1, 4‐Dehydrogenation with a Two‐Coordinate Cyclic (Alkyl)(amino)silylene. Issue 39 (24th June 2019)

• Record Type: Journal Article
• Authors: Koike, Taichi; Kosai, Tomoyuki; Iwamoto, Takeaki
• Is Part Of: Chemistry. Volume 25:Issue 39(2019)
• Page Start: 9295
• Page End: 9302
• Publication Date: 2019-06-24
• Subjects: aromatic compounds -- C−H activation -- dehydrogenation -- main-group elements -- reaction mechanisms -- silylenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201901407
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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. Abstract : Silylene reactions : A two‐coordinate cyclic (alky)(amino)silylene (CAASi) facilitates the regioselective 1, 4‐dehydrogenation of numerous 1, 4‐cyclohexadiene and 9, 10‐dihydroanthracene derivatives (see scheme). Experimental and computational studies indicated that the reactions proceed mainly through a stepwise hydrogen‐abstraction mechanism.