Gentlemen, start your engines! A starter system for the smallest molecular motor known so far, B13+, has been prepared. An external laser field of circular polarized light with a tuned frequency is used to trigger the rotation of the inner and outer rings of the planar π-aromatic double-ring system (see picture). Can this idea be transferred to other systems in nanotechnology?
Shape matters: Changes, which are brought about by irradiation, to the properties of a medium have been of immense interest not only in terms of basic science, but also for applications such as data storage media and molecular devices. In the light of a recent publication reporting a photodriven liquid to liquid crystalline transformation (see figure), an overview of similar transitions is presented.
Functionalized dihydrobenzofuran derivatives can be obtained by intramolecular alkoxycyanation and alkoxyacylation of alkenes (see scheme). In both transformations, selective activation of an OFG bond is accomplished by using a transition-metal catalyst. These transformations represent a conceptually new approach to metal-catalyzed alkene difunctionalization.
Radical chaperone: Recent research reveals how the 5′-deoxyadenosyl radical (see structure) is generated by homolysis of the CoC σ-bond of enzyme-bound coenzyme B12 and how it is guided to the substrate through pseudorotation of the ribose moiety and hydrogen-bonding interactions.
Catching a plane: A new strategy for stabilizing the BC bonds in boron-containing π-conjugated materials has been demonstrated. Encasing the boron in a rigid, planarized environment (see scheme) has been shown by Yamaguchi and co-workers to give air- and moisture-stable organoboranes that bring the boron's p orbital into full conjugation with the organic π framework.
Trap it: A combination of aminocatalysis with H-bonding activation is used in two new approaches to carry out formal enantioselective organocatalyzed [2+2] cycloaddition reactions. This cooperative catalysis solves the inconveniences associated with this transformation. These two new reactions will open opportunities to find reactivities involving other organocatalytic cycloadditions.
Finger on the pulse: A systematic experimental study of pulse-coupled chemical oscillators with delay has confirmed a surprisingly large number of theoretical and mathematical predictions (see the dynamics for a pair of pulse-coupled oscillators; AP=antiphase (AP) and IP=in-phase oscillations, C=complex bursting dynamics, and OS=oscillator suppression). These results have implications for neuroscience and other biological fields.
Complement for Fischer: An efficient palladium-catalyzed indole synthesis proceeds by the intramolecular cross-dehydrogenative coupling of N-aryl imines under mild conditions using molecular oxygen as the sole oxidant. This practical method relies on anilines and ketones as starting materials (and thus the same retrosynthetic disconnection as the Fischer indole synthesis) and will likely become a popular route.
Using molecules as individual components in electronic devices promises the ultimate in miniaturization coupled with the flexibility of organic synthesis to tune the individual component. Examination of metal/molecule/metal junctions (see figure) show that organic functionality has little effect on the conductivity and rectification behavior of molecular electronic junctions, thus questioning the possible tunability of molecular electronic devices.
Quite a process: Recent pioneering reports establishing proof of concept for conducting lithiation chemistry to produce organoboron products in a continuous fashion are highlighted (see scheme).
Impressive and elegant approaches to the enantioselective synthesis of spiroketals starting from achiral substrates have been described recently. These strategies based on transition-metal catalysis and organocatalysis hold great potential for further applications.
Simple, but effective: The asymmetric heterodimerization of two different ketenes (see scheme) has been developed 65 years after the first seminal studies on ketene dimerization. The key to sufficiently suppressing the competing homodimerization of the monosubstituted ketene donor (shown in blue) is its slow addition to the disubstituted acceptor (shown in red).
With or without you: Chiral secondary alkylboronates can now be accessed by highly enantioselective catalytic methods including conjugate addition under metal-free conditions with an NHC catalyst, and also iridium-catalyzed hydrogenation. These methods reinforce the potential of secondary alkylboronates as ideal and universal chiral building blocks for bond formation to sp3 carbon atoms.
On/off catalysts: Control over catalysis can be gained when the catalysts can be switched between an active and a nonactive state by external stimuli. In recent examples, orthogonal signals—light, pH, or the addition of ions—are used for the switching.
A common golden thread: The exact role of dinuclear gold species in catalysis has recently attracted considerable attention. Such well-defined complexes can now be isolated and fully characterized and may assist in elucidating the exact action of gold centers in gold-catalyzed reactions. In view of the latest developments in this area, possibilities now abound in terms of mechanistic exploration and novel catalyst design.
Electron-deficient Michael acceptors can be used in reversible addition/elimination reactions with thiols. These electrophiles were used to convert a known irreversible kinase inhibitor into a covalent and reversible inhibitor. Such an approach might provide high-affinity binders with increased selectivity without the toxicological risks associated with irreversible protein modifications.
Come together: The joining of two miniature proteins binding different protein targets in a synthetic adaptor protein is a novel way to induce proximity between proteins. The formation of a ternary complex was shown to cause the phosphorylation of a noninherent substrate (hDM2) by the kinase Hck. The approach holds promise to become a genetically encodable system to redirect enzyme activities in vivo.
Colorful mixture: Three types of luciferin analogues, that is, alkylaminoluciferins, aminoselenoluciferin, and luciferins with a benzimidazole scaffold, have been reported (see scheme). These analogues show excellent bioluminescent properties and great potential in bioluminescence imaging.
Fields of gold: Recent developments in the field of gold catalysis, using an alkyne as a carbonyl equivalent is becoming an important chemical transformation, thus providing flexibility in synthetic planning of complex and sensitive natural products. Understanding of the reaction and new catalyst designs are providing new conditions that are amenable for late-stage synthetic intermediates.
Bending over backwards to build buckybowls and -balls? For the last two decades, flash vacuum pyrolysis of chloro- and bromoarenes has been the method of choice for intramolecular aryl–aryl couplings that afford geodesic polynuclear arenes (“buckybowls”) including fullerene C60. Recently, even fluoroarenes were subjected under relatively mild conditions to intramolecular CArCAr couplings by combining the cleavage of CArF with the formation of very strong SiF or AlF bonds (see picture; green C, white H).
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