Catalytic and mechanistic studies into the epoxidation of styrenes using manganese complexes of structurally similar polyamine ligands.

Two structurally similar polyamine ligands (7 and 8) have been prepared, which differ only by the presence of either a secondary or tertiary nitrogen donor within their N5 donor set. The ligands, in combination with iron and manganese salts, have been screened for their efficacy as catalysts for the epoxidation of styrene, using both hydrogen peroxide and peracetic acid as oxidants. Clear differences in activity between the two systems were observed, with 7 proving most effective in the presence of MnSO4 with H2O2, whereas ligand 8 proved to be effective with Mn(OTf)2, MnCl2 and Mn(ClO4)2 using peracetic acid as the oxidant.

Initial rate kinetic studies show an unexpected influence of para-substituents on the catalytic behaviour of manganese complexes of TMTACN in the epoxidation of styrenes with H2O2.

Investigations into the efficacy of a range of enantiomerically pure BINOL additives in the epoxidation of styrene substrates with a number of manganese catalysts prepared from the ligand 1,4,7-trimethyl-1,4,7-triazacyclononane, TMTACN, using hydrogen peroxide as the oxidant have revealed that there are fundamental differences in reactivity between apparently similar systems. Whilst no asymmetric induction was obtained in the styrene oxide products formed, the data obtained from initial rate kinetic studies appear to be consistent with a number of different catalytically active species operating, the nature of which are profoundly affected by the starting materials used.

Recent advances in catalytic asymmetric epoxidation using the environmentally benign oxidant hydrogen peroxide and its derivatives.

There has been a recent drive to develop asymmetric catalytic methods to produce epoxides using environmentally benign oxidants, especially hydrogen peroxide. This critical review discusses the advances that have been made using both metal-based and organocatalytic homogeneous catalysts (142 references).

Stereocontrolled synthesis of trans-cyclopropyl sulfones from terminal epoxides.

Treatment of a range of (enantiopure) epoxides with the sodium salt of diethyl (phenylsulfonyl)methylphosphonate in DME at 140 degrees C for 4 h gives a variety of (enantiopure) trans-cyclopropyl sulfones with high diastereoselectivity.