Die Erzeugung von Br2 durch die Oxidation von Bromid-Ionen an der Anode und die Reduktion von molekularem Sauerstoff an der Kathode zu H2O2 führte in der Summe zur Erzeugung von zwei Molekülen Br2 (= vier-Elektronen Oxidation) wobei lediglich zwei Elektronen durch die Lösung geschickt wurden. Das molekulare Brom wurde zur Bromierung von Alkenen genutzt woraufhin eine lineare gepaarte Elektrolyse verwirklicht wurde, welche Stromausbeuten von bis zu 200% aufweist. Zudem gelang die Diiodierung von Cyclohexen als auch die elektrophile aromatische Bromierung eines Elektronen-reichen Aromaten mit jeweils 168% Stromausbeute.

Allylsilanes undergo highly regioselective intermolecular alkene hydroaminoalkylation with secondary amines in the presence of a titanium mono(formamidinate) catalyst. Corresponding reactions of a suitable allyl(2-bromophenyl)silane which exclusively deliver the branched hydroaminoalkylation products combined with a subsequent Buchwald-Hartwig amination result in the development of an elegant one-pot procedure for the synthesis of literature-unknown silicon analogues of 1,5-benzodiazepines, the so-called 1,5-benzoazasilepines.

The electrochemical carbon–carbon bond formation process between β-keto esters and silyl enol ethers was investigated utilizing manganese salts. The tricarbonyl compounds were generated in moderate to good yields under neutral conditions. Control experiments revealed that an electro-generated base at the cathode is important. Electroanalytical measurements with a Mn­(TPA) complex suggested that the oxidation of the silyl enol ether is the first step in the oxidation process initiated by a corresponding Mn­(IV) species.

Cyclic α‐(ortho‐iodophenyl)‐β‐oxoesters were converted in a ring‐expanding transformation to furnish benzannulated cycloalkanone carboxylic esters. The reaction sequence started by electrochemical reduction of the iodoarene moiety. In a mechanistic rationale, the resulting carbanionic species was adding to the carbonyl group under formation of a strained, tricyclic benzocyclobutene intermediate, which underwent carbon–carbon bond cleavage and rearrangement of the carbon skeleton by retro‐aldol reaction. The scope of the reaction sequence was investigated by converting cyclic oxoesters with different ring sizes yielding benzocycloheptanone, ‐nonanone and ‐decanone derivatives in moderate to good yields. Furthermore, acyclic starting materials and cyclic compounds carrying additional substituents on the iodophenyl ring were submitted to this reaction sequence. The starting materials for this transformation are straightforwardly obtained by conversion of β‐oxoesters with phenyliodobis(trifluoroacetate).

The electrochemical, oxidative Umpolung reaction of silyl enol ethers utilizing simple iodide salts for the synthesis of α-amino ketones is described. The products were isolated in excellent yields of up to 100%, and various functionalized starting materials were accepted in an undivided electrochemical cell design. Moreover, a sensitivity assessment to ensure an improved reproducibility of the reaction and cyclic voltammetry experiments were performed to postulate a plausible reaction mechanism on their basis.