Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction

Abstract

The electrophilic ipso-substitution of trimethylsilyl-substituted benzene derivatives into nitrosobenzene derivatives is reported. The optimization of the reaction conditions was performed for moderately electron-deficient, electron-rich, and sterically hindered starting materials by varying reaction time, temperature, and equivalents of NOBF. Also, a stable intermediate of the nitrosation reaction could be characterized by F NMR which can be assigned to a NO adduct with the nitrosobenzene derivative. This complex decomposes upon aqueous workup and liberates the desired nitrosobenzene derivative.

Gold-Catalyzed Chemoselective Couplings of Polyfluoroarenes with Aryl Germanes and Downstream Diversification

“…Indeed, using our previously developed Pd (I) dimer enabled methodology, , we were able to selectively and quantitatively alkylate and/or arylate the C–I and C–Br sites at room temperature in less than 5 min in the presence of oxygen using the air-stable Pd (I) dimer (see Figure , compounds 33 , 35 , and 36 ) . Similarly, the SiMe 3 functionality was readily halogenated, nitrosylated, and acetoxylated, , to give compounds 13 , 29 , and 30 in high yields. Light-activated arylation of SiMe 3 was also efficient.…”

“…We envisioned that a very rapid coupling method might outcompete C−F activation even for the most nucleophilic coupling partners, such as Grignard reagents. Indeed, using our previously developed Pd (I) dimer enabled methodology, 10,32 we were able to selectively and quantitatively alkylate and/or arylate the C−I and C−Br sites at room temperature in less than 5 min in the presence of oxygen using the air-stable Pd (I) dimer (see Figure 3,compounds 33,35,and 36). 33 Similarly, the SiMe 3 functionality was readily halogenated, nitrosylated, and acetoxylated, 34,35 to give compounds 13, 29, and 30 in high yields.…”

Reactive nitrogen species: Nitrosonium ions in organic synthesis

“…In 2018, Hilt and co-workers reported a related transformation for the nitrosodesilylation of 21 (Scheme 8b). [31] A shared feature of both methods is the fast reaction rate. According to the proposed mechanism for both approaches, a shared pathway for the nitrosation exists via ipso-substitution of the leaving group.…”

C−H Hydroxylation of Quinoxalin‐2(1H)‐ones through ipso‐Substitution Using tert‐Butyl Nitrite

“…For example, ipso‐ nitration of aryl boronic acids, [6] and carboxylic acids [6d,7] has been achieved by utilizing suitable nitro sources. Parallelly, ipso ‐nitrosation of trimethylsilyl benzene has been cataloged [8] . The key advantage of the ipso ‐substitution strategy is to overcome the regioselectivity issues.…”

“… a) Approaches of ipso ‐nitration [6c] and nitrosation [8] via electrophilic substitution reactions. b) C‐5 Hydroxylation of 8‐aminoquinoline amides [11] .…”