Robert W. Murray

A new synthesis of nitro compounds using dimethyldioxirane

Abstract Dimethyldioxirane oxidizes primary amines to nitro compounds in a facile, mild, high yield process.

Methyltrioxorhenium-Catalyze CH insertion reactions of hydrogen peroxide

Abstract Methyltrioxorhenium catalyzes the CH insertion reaction of hydrocarbons by hydrogen peroxide. In suitable substrates the reaction is stereospecific with retention.

Oxidation of organonitrogen compounds by the methyltrioxorhenium-hydrogen peroxide system

Abstract Methyltrioxorhenium catalyzes the reaction of hydrogen peroxide with organonitrogen compounds. The reactions are facile and high yield at room temperature or below. The observed chemistry is similar to that previously described by us using dimethyldioxirane as the oxidant.

Oxidation of [60]fullerene by the methyltrioxorhenium-hydrogen peroxide system

Abstract Methyltrioxorhenium catalyzes the oxidation of C 60 by hydrogen peroxide to give C 60 O. The reaction continues to produce C 60 O 2 and higher oxides. The yield of C 60 O represents a modest improvement over that given by other methods. The reaction conditions can be manipulated to give high conversions of the C 60 .

Solvent tuning of diastereoselectivity in dimethyldioxirane epoxidation reactions

Diastereoselectivity in the epoxidation of cyclohex-2-en-1-ol shows a remarkable solvent dependence. In some solvent systems the substrate OH group apparently can provide a cis selectivity through H-bonding.

A convenient high yield synthesis of nitroxides

Abstract Appropriate secondary amines are readily converted to nitroxides by dimethyldioxirane in a rapid, convenient, and essentially quantitative process.

A High Yield One Step Synthesis of Hydroxylamines

Abstract Oxidation of secondary amines with dimethyl-dioxirane gives hydroxylamines in a simple, one step and high yield process.

Gas phase generation of O2(+Δg) at atmospheric pressure by direct laser excitation☆

Abstract O 2 ( 1 Δ g ) was generated in the gas phase at atmospheric pressure by direct laser excitation. A Holobeam model 255 Nd—YAG laser with an output at 1065 nm was used to achieve the transition O 2 ( 3 Σ g − , v = 0) → O 2 ( 1 Δ g , v = 1) The mean lifetime τ of the resulting excited oxygen species in the gas phase at atmospheric pressure was measured to be 0.124 ± 0.012 s. This corresponds to a bimolecular rate constant k 2 for the overall reaction O 2 ( 1 Δ g , v = 1) + O 2 ( 3 Σ g − ) → 2O 2 ( 3 Σ g − ) of (3.3 ± 0.4) × 10 −19 molecule −1 cm 3 s −1 , a factor of 10 below the currently accepted value for ground state oxygen deactivation of singlet oxygen. Possible reasons for this difference are discussed.

Formation of a K-region arene oxide by intramolecular 0 atom transfer

Abstract Intramolecular reaction of the carbonyl oxide 1-benzoylphenanthrene oxide leads to the K-region oxide 1-benzoyl-9,10-epoxy-9,10-dihydrophenanthrene.

EVIDENCE FOR ELECTROPHILIC CHARACTER IN OXYGEN ATOM TRANSFER BY CARBONYL OXIDES

Abstract— Naphthalene was oxidized by carbonyi oxides produced by singlet oxygen oxidation of p, p‐disubstituted diphenyldiazomethanes. Yields of naphthol products correlate with Hammett σ constants giving ρ=+0.93. The results are interpreted as indicating the electrophilic character of these oxidations.