A series of azomethine-based HTMs is synthesized using simple condensation chemistry. Their photovoltaic performance and moisture barrier properties are presented.

We report herein versatile, transition metal-free and additive-free (hetero)­aryl–aryl coupling reactions promoted by the oxidative electrocoupling of unsymmetrical tetra­(hetero)­arylborates (TABs) prepared from ligand-exchange reactions on potassium trifluoroarylborates. Exploiting the power of electrochemical oxidations, this method complements the existing organoboron toolbox. We demonstrate the broad scope, scalability, and robustness of this unconventional catalyst-free transformation, leading to functionalized biaryls and ultimately furnishing drug-like small molecules, as well as late stage derivatization of natural compounds. In addition, the observed selectivity of the oxidative coupling reaction is related to the electronic structure of the TABs through quantum-chemical calculations and experimental investigations.

Spurred on by the recent emerging interest from the chemical community for unsaturated four-membered heterocycles, an unprecedented approach to nitrogen-containing four-membered rings has been designed. 3,4-Disubstituted 2-azetines were synthesized from commercially available substrates, allowing for a straightforward access to a new library of chiral functionalized azetidines and amino alcohols. This original approach was applied to efficiently prepare functionalized azobenzenes, an emerging class of molecules with a large potential in photopharmacology.

Conventional methods carrying out C(sp 2 )−C(sp 2 ) bond formations are typically mediated by transition‐metal‐based catalysts. Herein, we conceptualize a complementary avenue to access such bonds by exploiting the potential of electrochemistry in combination with organoboron chemistry. We demonstrate a transition metal catalyst‐free electrocoupling between (hetero)aryls and alkenes through readily available alkenyl‐tri(hetero)aryl borate salts (ATBs) in a stereoconvergent fashion. This unprecedented transformation was investigated theoretically and experimentally and led to a library of functionalized alkenes. The concept was then carried further and applied to the synthesis of the natural product pinosylvin and the derivatization of the steroidal dehydroepiandrosterone (DHEA) scaffold.

Described is the in situ formation of triorganocerium reagents and their application in catalyst‐free Zweifel olefinations. These unique cerium species were generated through novel exchange reactions of organohalides with n‐Bu3Ce reagents. The adequate electronegativity of cerium allowed for compensating the disadvantages of both usually functional‐group‐sensitive organolithium species and less reactive organomagnesium reagents. Exchange reactions were performed on aryl and alkenyl bromides, enabling enantiospecific transformations of chiral boron pinacol esters. Finally, these new organocerium species were engaged in selective 1,2‐additions onto enolisable and sterically hindered ketones.