Synthetic Chameleon Turns into Oximes, Nitrones, and Hydroxylamines when Exposed to Blue Light.

A metal-free, user-friendly photochemical transformation of nitroalkanes to oximes, nitrones, and hydroxylamines has been developed. The visible-light-induced reactions are catalyzed by the readily available photoredox organocatalyst 4CzIPN and use inexpensive amines as reductants. Broad in scope and tolerant of multiple functional groups and heterocycles, the transformation proceeds under mild conditions. Its synthetic potential was demonstrated in the formal total synthesis of amathaspiramide F. A basic insight into the reaction mechanism was gained with the help of an NMR study.

Visible-Light-Promoted Cross-Coupling of N-Alkylpyridinium Salts and Nitrostyrenes.

A stereoselective, denitrative cross-coupling of ß-nitrostyrenes with N-alkylpyridinium salts for the preparation of functionalized styrenes has been developed. The visible-light-induced reaction proceeds without any catalyst at ambient temperature. Broad in scope and tolerant to multiple functional groups, the moderately yielding transformation is orthogonal to several traditional metal-catalyzed cross-couplings.

Denitrative Cross-Couplings of Nitrostyrenes.

Interestingly, ß-nitrostyrenes, typically bench stable compounds, are highly promising cross-coupling partners, due to their excellent availability and well understood reactivity. In this review, we report on the discovery and advancements, in the field of stereoselective, denitrative cross-couplings of ß-nitrostyrenes with miscellaneous organic reagents. The rapidly expanding field offers alternative access to a broad range of functionalized alkenes, including ß-alkylated styrenes, chalcones, stilbenes, cinnamic acids, and conjugated sulfones and phosphonates. The most important mechanistic pathways are briefly discussed, to familiarize readers with the elementary reactions occurring during the coupling.

Crystallization Does It All: An Alternative Strategy for Stereoselective Aza-Henry Reaction.

An efficient and experimentally straightforward method for the stereoselective synthesis of a variety of ß-nitro-α-amino carboxylic acids via aza-Henry (nitro-Mannich) reaction of aldimines is disclosed, yielding either anti- or a rarely reported syn-configuration. The reaction operates directly on free glyoxylic acid and generates imine species in situ. Crystallization-controlled diastereoselectivity enables isolation of the target compounds in high enantio- and diastereomeric purities by a simple filtration.