All in one pot! Radical, radical–ionic, and radical–organometallic MCR are highly convergent processes, representing a useful pathway to molecular and structural diversity (see scheme). This concept article highlights recent developments in the field and shows the potential of the strategy for the economical elaboration of various kinds of organic substrates.
Stable complexes : An extremely air‐stable μ2‐hydroxy‐bridged binuclear hafonocene perfluorooctanesulfoante complex shows high catalytic efficiency in Lewis acid‐catalyzed reactions, such as esterification, Friedel–Crafts acylation, the Mukaiyama aldol reation, and the allylation of aldehyde (see scheme).
Switching characteristics: The 633 nm wavelength of an He–Ne laser is used to fabricate holographic transmission gratings in polymer‐dispersed liquid‐crystal cells. The microstructure and diffraction efficiency (η) both improve with increasing functionality (see figure). For functionalities of 2.5 or more, η approaches 34 % and can be switched off with electric fields of about 20 MV m?1.
Radical observation : Time‐resolved magnetic‐field effects yield a very detailed picture of electron‐transfer quenching in micelles and of the fate of the resulting radical‐ion pairs. The system xanthone/DABCO (A/D, see figure) permits a separation of the different static and dynamic quenching pathways and a distinction between bulk and surface diffusion.
Going through the phases : The title reaction was found to proceed by an initial base‐mediated isomerization to allenyl esters and subsequent phase transfer catalyzed alkylation at the α position of the ester (see scheme).
Regioselective, stereoselective : The convergent coupling of allylic alcohols with imines to deliver stereodefined homoallylic amines is described (see scheme). The process proceeds with net allylic transposition without the intermediacy of allylic organometallic reagents. Two stereodefined centers and a geometrically defined di‐ or trisubstituted alkene are forged with high selectivity.
Secondary, but second to none : The use of secondary alkyl halides in transition‐metal‐catalyzed cross‐coupling reactions (see scheme) has advanced significantly over the last five years. Selected examples of these transformations are examined, including mechanistic and stereochemical aspects.
Open sesame : Aptamer–substrate complexes activate the coherent operation of two tweezers that act as a “SET–RESET” logic system. Each tweezer cycles between a fluorescent open state and a closed quenched state (Q=quencher, F=fluorophore) when triggered by adenosine monophosphate (AMP) and adenosine deaminase (AD).
From imines to amines through catalysis by IrI complexes of a new type of P,N ligand (see scheme): This reaction affords the corresponding optically active amines with up to 98 % ee and has also been used with perfect stereoselectivity in the asymmetric synthesis of sertraline ( 1 ), an important antidepressant chiral drug.
Tungsten tryst : A 4‐H‐butatrienylidene complex of tungsten was successfully isolated and structurally characterized. It undergoes a unique self‐coupling, which leads to a dimer (see picture; P pink, O red) with a cross‐conjugated π system and with electrochemically and magnetically active metal centers.
