Herein, we report the redox-neutral allylation of aldehydes with readily available electron-rich allyl (hetero-) arenes, β-alkyl styrenes and allyl-diarylamines. This process was enabled by the combination of photoredox and chromium catalysis, which allowed a range of homoallylic alcohols to be prepared with high levels of selectivity for the anti diastereomer. Mechanistic investigations support the formation of an allyl chromium intermediate from allylic C(sp)-H bonds and thus significantly extends the scope of the venerable Nozaki-Hiyama-Kishi reaction.

The concept of reductive radical-polar crossover (RRPCO) reactions has recently emerged as a valuable and powerful tool to overcome limitations of both radical and traditional polar chemistry.

The discovery and application of dearomative cascade photocatalysis as a strategy in complex molecule synthesis is described. Visible-light-absorbing photosensitizers were used to (sequentially) activate a 1-naphthol derived arene precursor to divergently form two different polycyclic molecular scaffolds through catalyst selective energy transfer.

The direct conversion of feedstock chemicals into value-added products is of broad interest in chemical research. Herein, we present a regioselective and diastereoselective three-component dialkylation of feedstock 1,3-dienes with Hantzsch esters and aldehydes for the synthesis of homoallylic alcohols. The reaction is enabled by dual photoredox and chromium catalysis and can also be performed enantioselectively by employing chromium-bisoxazoline complexes.