Thermal .alpha.-deoxysilylation of N,O-bis(trimethylsilyl)-N-phenylhydroxylamine

Allylic Amination of Unactivated Olefins by Nitroarenes, Catalyzed by Ruthenium Complexes. A Reaction Involving an Intermolecular C−H Functionalization

“…The byproduct anilines are all commercial products and were identified by comparison of their CG and CG−MS spectra with those of authentic samples. Compounds 1c , 1d , 1e , 5 , and 6 14 are known compounds and were identified by their mass spectra and by comparison of the 1 H spectra of the isolated compounds with those reported in the literature and, in the case of 5 , by elemental analysis. The allylamines 1a − j were isolated from the reaction mixtures by column flash chromatography on silica (eluant CH 2 Cl 2 /hexane).…”

Direct Synthesis of Unprotected Indolines Through Intramolecular sp3 C−H Amination Using Nitroarenes as Aryl Nitrene Precursors

“…To verify this hypothesis experimentally, we initiated our investigation using phosphines and phosphites as oxophilic reducing reagents to obtain the desired 2‐phenylindoline ( 2 a ), however only little product was obtained using these reductants (See Supporting Information). We next turned our attention to the organosilicon‐based reagent N,N’ ‐bis(trimethylsilyl)‐4,4’‐bipyridinylidene (Si‐DHBP), which has been recently proposed to generate free nitrenes in the reduction of nitroarenes to anilines [60,69] . Gratifyingly, we observed that the reaction of 1.0 equivalent of 1‐nitro‐2‐phenethylbenzene ( 1 a ) as an aryl nitrene precursor along with 2.0 equivalents of Si‐DHBP as a reductant produced the desired 2‐phenylindoline product in 41 % 1 H NMR yield at 120 °C for 24 h using chlorobenzene as a solvent.…”

“…We next turned our attention to the organosilicon-based reagent N,N'-bis(trimethylsilyl)-4,4'-bipyridinylidene (Si-DHBP), which has been recently proposed to generate free nitrenes in the reduction of nitroarenes to anilines. [60,69] Gratifyingly, we observed that the reaction of 1.0 equivalent of 1-nitro-2-phenethylbenzene (1 a) as an aryl nitrene precursor along with 2.0 equivalents of Si-DHBP as a reductant produced the desired 2-phenylindoline product in 41 % 1 H NMR yield at 120 °C for 24 h using chlorobenzene as a solvent. The metalfree sp 3 CÀ H amination reaction using nitroarenes as nitrene precursors was further optimized by evaluating various reaction parameters (for detailed optimization studies, see Supporting Information).…”