Oxidations by methyl(trifluoromethyl)dioxirane. 2. Oxyfunctionalization of saturated hydrocarbons

Wenn C‐H‐Bindungen sprechen könnten – selektive Oxidationen von C‐H‐Bindungen

“…Eine Oxidation durch kleine Reagentien (z. B. TFDO) verläuft selektiv in der tertiären Position, [18] wogegen größere Reagentien (z. B. ein Polyoxometallat) geringere Oxidationsgeschwindigkeiten in tertiären Positionen zur Folge haben [19] und somit eine Selektivität für die Methylengruppen erreicht werden kann.…”

A General and Efficient Method for the Monohydroxylation of Alkanes

“…Dipl. (2), and the CH, group attached to C(2), suggesting the formation of a 1 : 1 cisltrans mixture for 1 b. The reaction of an equimolar mixture of 5a and 5b with diethylzinc gives a mixture of products.…”

“…['] The cyclic peroxide methyl(trifluoromethy1)dioxirane (1) has been revealed as a selective and very efficient oxidant for alkanes under very mild conditions. [2] Dioxirane 1 discriminates tertiary C-H bonds in the presence of methylene and methyl groups to give tertiary alcohols with a remarkably high selectivity. However, methylene groups are oxidized to ketones, since the secondary alcohol produced in the first oxygen transfer step reacts with 1 laster than the starting alkane.…”

Synthesis and X-Ray Crystal Structure of the First Pure and Air-Stable Salt of Peroxymonosulphuric Acid: (Ph)4PHSO5

“…As an example, triple salt (2) is used for both the oxidation of water-soluble substrates [9] and for oxidations catalyzed by metal porphyrins in two-phase systems [10]. Moreover, olefin epoxidations and alkane hydroxylations by (2) via the formation of a intermediate dioxirane have been accomplished [11]. In order to extend the use of monopersulphate to organic solvents, the lipophilic salt (3) has been prepared by extracting aqueous solutions of (2) with organic solutions of tetrabutylammonium inorganic salts [12].…”