The aim of this review is to highlight the rich chemistry of α‐haloamides originally mainly used to discover new C−N, C−O and C−S bond forming reactions, and later widely employed in C−C cross‐coupling reactions with C(sp³), C(sp²) and C(sp) coupling partners. Radical‐mediated transformations of α‐haloamides bearing a suitable located unsaturated bond has proven to be a straightforward alternative to access diverse cyclic compounds by means of either radical initiators, transition metal redox catalysis or visible light photoredox catalysis. On the other hand, cycloadditions with α‐halohydroxamate‐based azaoxyallyl cations have garnered significant attention. Moreover, in view of the important role in life and materials science of difluoroalkylated compounds, a wide range of catalysts has been developed for the efficient incorporation of difluoroacetamido moieties into activated as well as unactivated substrates.

Molecular switches based on the N-alkylated indanylidene-pyrroline (NAIP) framework mimic some of the outstanding double bond photoisomerization properties of retinal Schiff bases in rhodopsin, most notably, the occurrence of vibrational coherences in the excited and photoproduct ground states. Focusing on the zwitterionic NAIP switch and using broadband transient absorption spectroscopy, our previous investigation of the Z to E photoisomerization dynamics is now extended to the study of the backward E to Z photoisomerization and to the role of the solvent on the vibrational coherence accompanying the photoreaction. Despite very similar signatures of excited-state vibrational coherence and similar isomerization times, the backward reaction has a significantly smaller isomerization yield than the forward reaction, and most interestingly, does not display ground state coherences. This indicates that both the quantum yield and vibrational dephasing depend critically on the photochemical reaction path followed to reach the ground potential energy surface. In addition, investigation of the effect of the solvent viscosity shows that vibrational dephasing is mainly an intramolecular process.

Organocatalytic asymmetric domino sulfa-Michael/aldol condensation reactions between 1,4-dithiane-2,5-diol (the dimer of mercaptoacetaldehyde) and cinnamaldehydes were efficiently promoted by (S)-diphenylprolinol TMS ether in the presence of bile acid derivatives, leading to hitherto unknown 4,5-dihydrothiophene-2-carbaldehydes in moderate to good yields and good enantioselectivities.