The rhodium(II)-catalyzed aziridination of olefins with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda³-iodane

Fe-Catalyzed Aziridination Is Governed by the Electron Affinity of the Active Imido-Iron Species

“…While similar correlations are obtained for the two reactions, both the reduced absolute value of the slope and the necessary inclusion of resonance effects indicate that albeit aziridination is clearly dominated by inductive effects, resonance effects play a minor but noticeable role (see below). Dominant inductive effects were also revealed by Hammett correlations reported for Fe catalysts by Che and colleagues 39 and Jensen and colleagues, 40,44 for Cu catalysts by Muller and colleagues 71 and Chang and colleagues, 72 and for dirhodium tetraacetate by Muller and colleagues. 71…”

“…Dominant inductive effects were also revealed by Hammett correlations reported for Fe catalysts by Che and colleagues 39 and Jensen and colleagues, 40,44 for Cu catalysts by Muller and colleagues 71 and Chang and colleagues, 72 and for dirhodium tetraacetate by Muller and colleagues. 71…”

Mechanistic Insights into the Substrate‐Controlled Stereochemistry of Glycals in One‐Pot Rhodium‐Catalyzed Aziridination and Aziridine Ring Opening

“…It is generally accepted that metal-bound nitrenes are involved in metal-catalyzed aziridination and even though those iodinane complexes are very nitrene-like, they are not reactive enough to attack the alkene before dissociation of PhI. [21] Espino and Du Bois [3a] and Müller et al [10,22] suggested that the direct binding of N and Rh atoms could occur in this process to give the reactive nitrene species without any transition states involved. As shown in Figure 2, the formation of an Rh 2 -iodinane intermediate of series 4, denoted as Ad1A C H T U N G T R E N N U N G (4 S), is energetically favored by a negative DG value (À9.6 kcal mol À1 at BPW91/BSI).…”

Rhodium(II,II) Dimer as an Efficient Catalyst for Aziridination of Sulfonamides and Amidation of Steroids

“…Nitrogen-atom transfer reactions catalyzed by transition-metal complexes are among the most appealing methodologies for the synthesis of amines and amine derivatives. − The rhodium(II,II) dimer has been proven to be a versatile catalyst for reactions involving CC bond addition and C−H bond insertion . In contrast to extensive investigations on C−C bond formation, the application of rhodium(II,II) dimer to C−N bond formation has received significantly less attention with, to the best of our knowledge, only a handful of publications reported to date. 1b,,, Furthermore, despite encouraging advances, challenges still remain: first, the turnover number for rhodium(II,II) dimer-catalyzed C−N bond formation remains rather low (<50) and needs to be improved; second, steroid starting materials have thus far received no attention as potential substrates.…”