The first highly enantioselective allylic–allylic alkylation of α,α‐dicyanoalkenes and Morita–Baylis–Hillman carbonates by dual catalysis of (DHQD)2AQN and (S)‐BINOL has been investigated. Excellent stereoselectivities have been achieved for a broad spectrum of substrates (d.r. > 99:1, up to 99 % ee). The multifunctional allylic products could be efficiently converted to a range of complex chiral cyclic frameworks. EWG=electron‐withdrawing group, (DHQD)2AQN=hydroquinidine (anthraquinone‐1,4‐diyl) diether, (S)‐BINOL =(S)‐(?)‐1,1′‐bi‐2‐naphthol.
Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well‐defined 41 helix in which the perylene molecules (see figure) form four “helter‐skelter‐like” overlapping pathways along which excitons and electrons can rapidly migrate.
Up and down: Differential sensing of serine and tyrosine is achieved with aligned CdS nanowire arrays by exploring the pH‐dependent PL behavior of the nanowire arrays toward exposure to the two amino acid solutions (see picture).
Two 4T: Low‐frequency micro‐Raman spectroscopy coupled with lattice dynamics calculations is an invaluable tool for investigating polymorphism in organic semiconductors. The Raman spectra of the low‐temperature (LT) and high‐temperature (HT) polymorphs of α‐quaterthiophene (4T) are presented and interpreted (see picture). Raman mapping is applied to investigate the phase purity.
Gas storage : A new, sulfone‐functionalized dicarboxylate‐based ligand (see figure) is capable of directing the formation of novel metal–organic frameworks with unprecedented organic and inorganic secondary building units. A high CO2 uptake with remarkable selectivity over CH4, N2, and H2 was observed at near‐ambient temperature.
Cascade reactions : Lewis acid catalyzed cascade reactions of 1,6‐diynes and 1,6‐enynes with arylvinylidenecyclopropanes produce polycyclic compounds and isopropylidene‐3,3‐diarylcyclobut‐1‐enylmethyl derivatives (see scheme) in good to high yields along with a PtCl2‐catalyzed cyclization and a Cu(OAc)2 ? H2O‐catalyzed Eglinton coupling reaction.
Two metal cooperation : A homodinuclear Co2–Schiff base complex Co2(OAc)2– 1 promoted the asymmetric 1,4‐addition of β‐keto esters to alkynones under solvent‐free conditions in air (see scheme). The reactions proceeded without air or moisture sensitivity in high yields and with high enantioselectivities (99–91 % ee) at room temperature under highly concentrated conditions (neat–20 M ) with 0.1–2.5 mol % catalyst loading.
Fast moving : A new pentad (see figure) composed of silicon phthalocyanine (SiPc), as electron donor, that is connected with two units of naphthalenediimide (NDI) and fullerene C60, as electron acceptors, undergoes fast and efficient charge‐separation processes via the NDI and SiPc singlet excited states.
Gone fishing : When propiophenone and related ethyl ketones are treated with morpholine in the presence of K3PO4, chlorobenzene, and [Ni(cod)2]/PMe3 catalyst, a carbon–nitrogen bond is formed selectively at the β position (see scheme; cod=cycloocta‐1,5‐diene). Secondary amines were employed as substrates to give the corresponding β‐enaminones.
Supramolecular protein polymers : When a heme moiety was introduced to the surface of an apo‐cytochrome b562(H63C) mutant, supramolecular polymers formed through noncovalent heme–heme pocket interactions. The incorporation of a heme triad as a pivot molecule in the protein polymer further led to a two‐dimensional protein network structure, which was visualized by tapping‐mode atomic force microscopy (see picture).
On an atomic scale and with high sensitivity, solid‐state NMR spectroscopy can provide information about the electronic spin density and coupling mechanisms in paramagnetic compounds. The picture shows how the hyperfine splitting collapses through relaxation. Insights into which compounds are suitable and which approximations have to be made are given.
First insights into the reaction between a Baylis–Hillman adduct and an allene moiety have been obtained from the novel domino heterocyclization/cross‐coupling reaction of α‐allenols and Baylis–Hillman acetates, which furnishes [(2,5‐dihydrofuran‐3‐yl)methyl]acrylate derivatives in moderate to good yields.
Phosphorus meets carbohydrates : Dimethyl phosphite reacts with ceric(IV) ammonium nitrate (CAN) to give phosphonyl radicals that add to glycals 1 . The derivatives 2 were isolated in high yields and during a subsequent Horner–Emmons reaction underwent an interesting elimination to give 3,6‐dihydro‐2H‐pyrans 3 . The short sequence with simple precursors is applicable to the transformation of hexoses, pentoses, and disaccharides. Bn=benzyl.
Constructing α‐stereogenic amides and ketones : The highly regioselective and enantioselective conjugate addition of 1,3‐dicarbonyl compounds to 1,4‐dicarbonyl but‐2‐enes has been developed with the chiral bicyclic guanidine as catalyst (ee values up to 97 %; see scheme).
Economical atoms : 2‐Cyclopenten‐1‐ones, 5‐alkylidenefuran‐2(5 H)‐ones and indan‐1‐ones have been synthesized by atom‐economic reductive cyclocarbonylation of internal alkynes with carbon monoxide catalyzed by [{RhCl(CO)2}2]/CO(NH2)2 in the presence of water (see scheme).
A new way to make a bang : Several functionalized 1‐ethyl‐5‐aminotetrazoles, 1‐ethyl‐5‐nitrimino‐tetrazoles, and copper complexes have been synthesized and their chemical and energetic properties have been comprehensively characterized. The compounds belong to all classes of “energetic materials”: explosives, propellants, and pyrotechnics.
