Sphere of destiny : Metal–organic spheres with remarkable encapsulation properties are readily prepared and their ability to host a wide range of guest species, including nanoparticles, fluorescent dyes, and quantum dots, is demonstrated. Both the metal–organic spheres and the encapsulated species maintain their fluorescent or magnetic properties, highlighting the importance of these systems as new multifunctional materials.
Simple addition : Copper(II) aqua complex 1 can be prepared in a one‐pot synthesis and is self‐assembled by H‐bond interactions. Complex 1 is shown to accelerate the nitroaldol reaction on water, which is a heterogeneous process, requiring no additive or base, and 1 can be recycled without loss of activity.
A Powerful Luminophore that comprises a centered pyrene acceptor with peripheral amine multidonors is described by J. S. Kim and co‐workers in their Communication on page 2522 ff. The electrochemiluminescence (ECL) efficiency and radical stability of pyrene, a poor ECL luminophore, is markedly improved as the number of peripheral multidonor units is increased in a series of compounds. The ECL enhancement was rationalized by photophysical and electrochemical studies, and theoretical calculations.
Forces to reckon with : Supramolecular complexes, such as the one shown, are normally based on a combination of different interactions such as ion pairing, hydrogen bonds, and stacking interactions. The not always simple characterization of the nature and strength of intermolecular forces provides assistance to the understanding of biomimetic systems, as well as for the design of synthetic receptors, drugs, and intelligent materials.
Throw your hat in the ring : A highly diastereoselective synthesis of the ABC rings of (?)‐norzoanthamine has been achieved starting from the (?)‐Hajos–Parrish ketone (see scheme). Three asymmetric quaternary carbon centers on the C ring were constructed by a 1,4‐addition, and an intramolecular Diels–Alder reaction provided a trans‐decalin scaffold on the AB rings.
Inner virtue : The reaction of [Mo0(GaCp*)6] with ZnMe2 yields the novel multinuclear zinc system [MoZn12Me9Cp*3] which geometrically resembles a classical Wade–Mingos cluster (with an interstitial molybdenum atom, see picture). In reality, its electronic structure features little direct Zn? Zn bonding, relying instead on Mo? Zn three‐center, two‐electron bonds spanning the body diagonals of the approximately icosahedral framework.
Catalytic convenience : The use of iridium or ruthenium catalysts for C? H bond activation has led to the addition reaction of trifluoromethylated compounds to alkenes (see scheme). This atom‐economical reaction occurs under neutral reaction conditions and without the formation of undesired defluorinated by‐products, even at high temperature.
Bi? O chemistry : A direct regioselective route to bismuth bis(amino)naphthalene compounds, incorporating Bi? O and Bi? C bonds is described, in which an amide precursor is treated with aldehydes, ketones, alkenes, and alkynes, leading to insertion into the Bi? NMe2 bond.
A porous copper coordination framework grew epitaxially as a single crystal on the surface of a single crystal of a porous zinc coordination framework, as described by S. Kitagawa and co‐workers in their Communication on page 1766 ff. The picture shows the structural relationship between the copper and zinc frameworks, which has been unveiled by synchrotron surface X‐ray diffraction measurements; in‐plane rotational epitaxial growth compensates for the different lattice constants of the two crystals.
“The most exciting thing about my research is to create new molecules and new concepts. When I was eighteen I wanted to be an industrial chemist. …?” This and more about Koop Lammertsma can be found on page 4670.
Metal–organic frameworks (MOFs) are one of the most important classes of material in current chemistry. One open question is what is the mechanism of their crystal growth? In situ atomic force microscopy (see image) can be used to look at the surface of crystals as they grow, revealing a number of interesting features and giving clues to the molecular species that are important in the growth mechanism.
No need for a metal : A combination of mass spectrometry and computational studies (density functional theory and coupled‐cluster methods) shows that [P4O10].+ is the first polynuclear nonmetal oxide cation that is capable of activating the C? H bond of methane at room temperature (see picture). This process represents a further example in the reactivity of oxygen‐centered radicals.
Excellent couplings : Recent developments in the metal‐catalyzed C? H activation of sp3 centers in an α position relative to an amine nitrogen atom are presented. Their reaction with alkenes to give alkylamines (hydroaminoalkylation) is also summarized (see general scheme).
“ Quat's” the story? N‐Aryl amides are effective directing/activating groups for chlorosilane Lewis acids. This aspect has been exploited for the development of the first simple and general method for the highly enantioselective Pictet–Spengler reaction of ketimines derived from α‐ketoamides leading to quaternary α‐amino acid derivatives (see scheme).
No bones about it : (?)‐Norzoanthamine, a promising candidate for an anti‐osteoporotic drug, was the target of a total synthesis (see scheme). The final bisaminal formation with AcOH/H2O gave the DEFG ring, while the cyclization precursor was prepared by installing the remaining bisaminal unit after oxidative cleavage of the cyclopentanol moiety.
Cooperative metal centers in a bimetallic catalyst facilitate the highly enantioselective ring opening of meso aziridines 1 with silyl nucleophiles (see scheme; TMS=trimethylsilyl). The 1,2‐azidoamides 2 and 1,2‐amidonitriles 3 obtained in this way in high yields and with up to 99 % ee are valuable precursors to enantiomerically pure 1,2‐diamines and β‐amino acids.
