Exerting control over the acyloin reaction.

A synthetic method for conducting the acyloin reaction using electron transfer in solution is reported. By linking two esters via their oxygen atoms, it was possible to perform crossed acyloin reactions between two different ester functionalities and display a high degree of preference for an intramolecular coupling process.

Electrosynthetic reduction of 1-iodoadamantane forming 1,1'-biadamantane and adamantane in aprotic solvents: insonation switches the mechanism from dimerisation to exclusive monomer formation.

The combination of ultrasound and electrochemistry -sonoelectrochemistry can produce a variety of effects within an electrochemical system including enhanced mass transport, in situ cleaning of an electrode surface, diminution of the diffusion layer, and possible induction of new reactions by sonochemical enhancement of follow-up reactions post-electron transfer. Herein, we show that ultrasound provides a useful extra dimension to electrosynthesis via a switch in the sonoelectroorganic mechanism in which dimerisation is disfavoured by virtue of convective mixing promoted by insonation. Under 'normal' voltammetric conditions the reduction of 1-iodoadamantane at a silver cathode in tetrahydrofuran (THF) and acetonitrile (ACN) involves a single electron forming a mixture of monomeric and dimeric products; 58%/THF, 50%/ACN adamantane and 39%/THF, 50%/ACN 1,1'-biadamantane, respectively.

Cryovoltammetrically probing functional group reductive cleavage: alkyl-sulfur versus aryl-sulfur bond cleavage in an alkyl naphthyl thioether under single electron-transfer is temperature switchable.

A series of single electron-transfer (SET) reactions on a naphthyl thioether have shown that the reductive cleavage mechanism changes at low temperatures and this selectivity is proved using an electrochemical analysis that mimics the SET reaction conditions.

An enzymatic approach to the desymmetrization of disubstituted pyrrolines.

The enzymatic desymmetrization of 2,2- and 2,5-disubstituted pyrroline compounds is reported in a procedure which gives access to both enantiomers in excellent enantiomeric excess and good yield. The enzyme reaction precursors are formed easily from two readily available substituted pyrroles using both ammonia (Na/NH3) and ammonia-free (Li/DBB) Birch reduction conditions.