Our recent work has provided new insights into the equilibria and species that exist in aqueous solution at different pHs for the boric acid - hydrogen peroxide system, and the role of these species in oxidation reactions. Most recently, (M. C. Durrant, D. M. Davies and M. E. Deary, Org. Biomol. Chem., 2011, 9, 7249-7254), we have produced strong theoretical and experimental evidence for the ex...

Introduction Since their discovery in the late 1960s, the [2,3]-sigmatropic rearrangements of sulfonium ylides have received considerable attention because of their applications in organic synthesis and their probable involvement in biochemical processes. The most common method for sulfonium ylide generation involves the removal of a proton from a sulfonium salt with a strong base. However, a m...

Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowe...

Crown ether complexation solubilizes organic and inorganic salts in nonpolar media. Induction of crystallization from such solutions can result in crystallization of the free salt rather than the complex. This affords the opportunity to examine solvent effects on the crystallization of salts and other polar materials, leading to the modification of crystal shape and lattice. This approach, whic...

Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just lik...

Cytochrome P-450 mono-oxygenase enzymes play a key role in the oxidative transformation in living systems. As one kind of cytochrome P-450 models, metalloporphyrins have been widely used in selective oxygenation of hydrocarbons under mild conditions. The chapter focuses on reviewing the biomimetic homogeneous oxidation of organic compounds catalyzed by metalloporphyrins with green oxidants such...

Transition-metal alkane-thiolates (i.e., organic salts with formula Me(SR)x, where R is a linear aliphatic hydrocarbon group, –CnH2n+1) undergo a thermolysis reaction at moderately low temperatures (close to 200 °C), which produces metal atoms or metal sulfide species and an organic by-product, disulfide (RSSR) or thioether (RSR) molecules, respectively. Alkane-thiolates are non-polar chemical ...