The Rate of Oxidation of Alicyclic Ketones with Perbenzoic Acid^1a

Baeyer–Villiger Oxidations with Hydrogen Peroxide in Fluorinated Alcohols: Lactone Formation by a Nonclassical Mechanism

“…Furthermore, it was surprising to see that camphor-a well-known substrate of the Baeyer±Villiger oxidation with peracids-was not significantly consumed. [1,2,13] These results clearly indicated that a mechanism different from the classical peracid-induced Baeyer±Villiger oxidation may be operative. To gain further insight, we performed the oxidation of 1 in [D 2 ]HFIP and monitored the reaction by 13 C NMR spectroscopy ( Figure 1).…”

“…The a values [12] were obtained by full DFT calculations on the QM model units and the full complexes. A triple-z basis set was used on ruthenium; [13] a polarized double-z basis set was used for all other elements. The 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 electrons of the ruthenium atoms, the 1s 2 2s 2 2p 6 electrons of the chlorine and phosphorus atoms, and the 1s 2 electrons of the carbon atoms were treated within a frozen-core approximation.…”

“…Treatment of isolated 3 in HFIP with catalytic amounts of strong acids (such as p-TsOH) resulted in rapid and quantitative rearrangement to 2. For example, monitoring of a solution of isolated 3 in dry [D 2 ]HFIP by 13 C NMR spectroscopy showed complete conversion within seconds (with evolution of heat; Figure 1, trace b). Upon addition of water to the HFIP solvent, the rearrangement becomes increasingly slow, and 4 becomes more and more prominent as a side product (Figure 1, trace c).…”

“…A set of auxiliary s, p, d, f, and g STO functions (STO ¼ Slater orbital) centered on all nuclei was used to fit the molecular density and present Coulomb and exchange potentials accurately in each SCF cycle (SCF ¼ self-consistent field). [13] The local density approximation by Vosko, Wilk, and Nusair, [14] and generalized gradient approximation were used with the BP86 functional. [15] Scalar relativistic corrections were added to the total energy.…”

Non-Metallic Ketone Compounds Catalyzed Selective Epoxidation of Styrene with Dry Air

“…Various strategies, methods and many effective catalytic systems have been developed for the preparation of epoxides from olefins [1][2][3][4][5][6][7][8][9][10][11]. Recently, the catalytic epoxidation with organic peroxides, H 2 O 2 , oxygen and air has become an especially attractive target.…”