Selective Alkane Oxidation

Beneficial Effect of Acetic Acid on the Formation of FeIII(OOH) Species and on the Catalytic Activity of Bioinspired Nonheme FeII Complexes.

“…Very efficient Oatom insertion reactions into alkenes or alkanes are observed when Fe V (O) oxidants are generated, i. e. following heterolytic cleavage of the Fe III (OOH) species. [20,21] However, the yields and distribution of products are not different enough to conclude that a switch in reactivity, from a homolytic OÀ O cleavage with ligands 1 and 2 to a heterolytic one with 3, is happening. Thus, even with the most electron rich ligand 3 the push electronic effect does not seem to be sufficient to promote a heterolytic OÀ O cleavage and the generation of a Fe V (O) species.…”

Electrophotocatalytic oxygenation of multiple adjacent C–H bonds

“…A particularly attractive strategy to synthesize such molecules is to convert relatively inert carbon-hydrogen (C-H) bonds that are ubiquitous in simple precursor molecules into C-O bonds directly, a process known as C-H oxygenation. [1][2][3][4][5][6] Nature follows this type of strategy for the synthesis of a plethora of secondary metabolites, such as the cancer therapeutic paclitaxel (Taxol), the antimalarial drug artemsinin, or the plant hormone brassinolide, by using enzymes to achieve selectivity between what can otherwise be di cult to distinguish C-H bonds (Fig. 1B).…”

“…Nevertheless, tremendous progress has been made in achieving controlled, site-selective C-H oxygenation reactions in complex settings. [1][2][3][4][5][6][10][11][12][13][14] However, it remains very di cult to achieve the oxygenation of multiple C-H bonds simultaneously, particularly if those bonds are adjacent to one another, where the risk of overoxidation is severe. The challenge then is to develop a chemical strategy that is strongly oxidizing enough to effect multiple C -H oxygenations yet selective enough to not result in destructive overoxidation of the substrate.…”