Mn aminopyridine oxidase mimics: Switching between biosynthetic-like and xenobiotic regioselectivity in C H oxidation of (-)-ambroxide

High‐Spin and Low‐Spin State Perferryl Intermediates: Reactivity‐Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)‐Sclareolide

“…These results witness that, besides steric effects, electronic effects may play important roles in directing the regio‐, as well as chemoselectivity of C−H oxidation of complex substrates of natural origin. We believe that finely tuning the reactivity of the oxidizing species can enhance the chemo‐ and regioselectivity of bioinspired catalyst systems of the Fe(PDP) family for the late‐stage oxofunctionalization of biologically relevant complex molecules, [2,3,19,27–30] and envision increasing efforts in this direction.…”

“…origin. We believe that finely tuning the reactivity of the oxidizing species can enhance the chemo-and regioselectivity of bioinspired catalyst systems of the Fe(PDP) family for the late-stage oxofunctionalization of biologically relevant complex molecules, [2,3,19,[27][28][29][30] and envision increasing efforts in this direction.…”

Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp3)–H functionalization promoted by electrophilic reagents

“…Within this framework, a detailed investigation of the role of catalyst structure in the oxidation of (À)-ambroxide with H 2 O 2 catalyzed by Mn complexes was recently carried out. 150 Competitive oxidation at C-1, C-2 and C-3 was observed when employing the [Fe( Me,Me Pytacn)] and [Fe(mcp)] catalysts. With the former one, formation of the corresponding 1-oxo, 2-oxo and 3-oxo products in a 1 : 4.6 : 6.0 ratio and overall 58% isolated yield was observed (entry 2).…”

A Predictably Selective Palladium-Catalyzed Aliphatic C–H Oxygenation

“…The highest remote/proximal ratio (32.1:1) in the series was found for bromoalkane 9, which picture is similar to that reported for hydroxylations mediated by Mn-based catalysts of the PDP family. 32 Then, the effect of the steric environment of the 3°C−H sites was tested using (−)-acetoxy-p-menthane 11 as substrate. The oxidation preferentially occurred at the less sterically hindered C1 site (Table 3).…”