C–H oxidation by platinum group metal oxo or peroxo species

Abstract

While C-H oxidation by ruthenium oxo compounds has been broadly applied in organic synthesis, examples of C-H oxidation by metal oxo complexes from the rest of the platinum group are still rare. We survey the preparation and reactivity of these late-transition metal oxo and peroxo complexes in this tutorial review.

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

“…Values k 7 [MeCN]/k 6 (0.08 M) and k 7 /k 6 (0.0044) are close to the corresponding parameters obtained for oxygenation of cyclohexane in acetonitrile with H 2 O 2 . The experimental data are in agreement with this dependence, which is shown in Figure 18A.…”

“…This review is devoted to functionalization of carbon-hydrogen bonds [1][2][3][4][5][6][7][8][9][10][11][12][13] in various organic compounds, which is a very important process both from academic and practical point of view. Replacing hydrogen atoms in carbon-hydrogen compounds by functional groups X leads to valuable functionalized C-X compounds (Scheme 1a).…”

RhIII‐Catalyzed C(sp3)H Bond Activation by an External Base Metalation/Deprotonation Mechanism: A Theoretical Study

“…The traditional intramolecular CMD mechanism, which is widely followed in CÀHb onda ctivation reactions, [1] is no longer valid in this case. Indeed, the excesso ff ree acetate anionsa llows easy deprotonation of the methyl group of the reactantd ue to the better basicityo ft he free acetate compared with ligated acetate.…”

“…[1] In addition to the common C(sp 2 )ÀHa ctivation reactiono fa renes and alkenes, attention hasg radually been shifted to C(sp 3 )ÀHa ctivation,w hich is more difficult to achieve due to poor reactivity and al ack of regioselectivity. Recently,W ang and co-workersr eported an ovel Rh III -catalyzed C(sp 3 )ÀHa ctivation of 8-methylquinoline followedby the insertion of an alkyne( see Scheme 1) in DMF.…”

Bioinspired oxidations of aliphatic C–H groups with H2O2 in the presence of manganese complexes

“…One has to distinguish, however, the Shilov chemistry (which is essentially a C-H activation coupled to oxofunctionalization of the resulting metal-carbon bond [9]) from biomimetic oxygenations aiming at mimicking the reactivity of natural metalloenzymes. As of today, iron complexes (eventually regarded as the closest precursors of natural iron monooxygenases) constitute probably the largest class of alkane hydroxylation-active "synthetic enzymes", whose structure-reactivity and selectivity peculiarities, as well as modes of action have been most extensively explored [3,[10][11][12][13][14][15][16][17][18][19][20].…”