SO2 capture and detection using a Cu(II)-metal-organic polyhedron.

The SO2 adsorption-desorption capacity at room temperature and 1 bar of the metal-organic polyhedron MOP-CDC was investigated. In addition, the qualitative solid-state absorption-emission properties of this material (before and after SO2 exposure) were measured and tested, and it demonstrated remarkable capability for SO2 detection. Our results represent the first example of fluorimetric SO2 detection in a MOP.

Catalytic cascade reactions by radical relay.

Radical cascade reactions are an attractive tool for the rapid construction of complex molecular architectures. Although a large number of powerful radical cascades have been developed, stoichiometric amounts of reagents and/or additives are often required to mediate these processes. Radical relay strategies, in which radical character is recycled, require only a catalytic amount of reagent and are particularly attractive as they promise cascades that are high in atom economy. This tutorial review highlights recent advances in this rapidly developing area by setting out and dissecting the reaction designs underpinning state-of-the-art processes involving radical relays. Advances in the field of radical relay cascades will open the door to more efficient synthesis with far-reaching benefits for the makers and end-users of complex molecules.

Samarium(II) folding cascades involving hydrogen atom transfer for the synthesis of complex polycycles.

The expedient assembly of complex, natural product-like small molecules can deliver new chemical entities with the potential to interact with biological systems and inspire the development of new drugs and probes for biology. Diversity-oriented synthesis is a particularly attractive strategy for the delivery of complex molecules in which the 3-dimensional architecture varies across the collection. Here we describe a folding cascade approach to complex polycyclic systems bearing multiple stereocentres mediated by reductive single electron transfer (SET) from SmI2. Simple, linear substrates undergo three different folding pathways triggered by reductive SET. Two of the radical cascade pathways involve the activation and functionalization of otherwise inert secondary alkyl and benzylic groups by 1,5-hydrogen atom transfer (HAT). Combination of SmI2, a privileged reagent for cascade reactions, and 1,5-HAT can lead to complexity-generating radical sequences that unlock access to diverse structures not readily accessible by other means.