College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
Published: August 2022
AI Article Synopsis
Article Abstract
An iron(II)-catalyzed nitrene transfer reaction of sulfoxides with -acyloxyamides has been developed, leading to the efficient construction of acyl sulfoximines with high functional-group compatibility. The current catalytic transformation was carried out under an air atmosphere at ambient temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. Application of the methodology was demonstrated by facile C-H acetoxylation and olefination using the acyl sulfoximine as the directing group.
Ru(II)-Catalyzed "On Water" direct aryl C(sp2)-H amidation of 2-arylbenzo[d]-thiazole/oxazole with acyl azide is reported under silver-free condition. Deuterium scrambling experiments suggested reversible C-H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C-H amidation except for PhCl in which case, however, inferior yield (31%) was obtained.
This paper describes a ferric nitrene/photoredox dual-catalyzed anti-Markovnikov ring-opening of epoxides under neutral conditions for providing α-substituted acetophenones. A DFT-based calculation supported the reaction regioselectivity. The catalytic system could also be applied to the formation of C-O and C-N bonds nucleophilic functionalization of benzylic C-H bonds.
Although nitrene chemistry is promising for the light-induced modification of organic compounds, the reactivity of large polycyclic aromatic compounds and the effects of their curvature remain unexplored. Irradiation of azidocorannulene () in methanol/acetonitrile followed by HCl addition produced diastereomers and . Azirine is apparently trapped by methanol to form diastereomeric acetal derivatives that are hydrolyzed with HCl to yield and '.
In this work, the annulation of acyl nitrene with alkynes is reported under photoredox/iron dual-catalysis for the synthesis of a series of isoquninalin-2-ones. The reaction is featured with a high reaction regioselectivity and good reaction generality. In particular, the resulting isoquinalin-2-ones could be structurally elaborated into several biologically interesting scaffolds.
The development of artificial metalloenzymes (ArMs) offers a potent approach to incorporate non-natural chemical reactions into biocatalysis. Here we report the assembly of Mn(salen)-based ArMs by embedding biotinylated Mn(salen) complexes into streptavidin (Sav) variants. Using commercially available nitrene and oxo transfer reagents, these biohybrid catalysts catalyzed the aziridination of alkenes and oxidation of benzylic C-H bonds with up to 19 and 146 turnover numbers.
