[2,3]‐Wittig Rearrangement of Enantiomerically Enriched 3‐Substituted 1‐Propenyloxy‐1‐phenyl‐2‐propen‐1‐yl Carbanions: Effect of Heteroatoms and Conjugating Groups on Planarization of an α‐Oxy‐Benzylcarbanion through a Double Bond

Don't get trapped : The effect of conjugating electron‐withdrawing groups and α‐anion‐stabilizing heteroatom substituents on configurational stability of chiral carbanions through a double bond was examined on the basis of extent of chirality transfer in intramolecular trapping in [2,3]‐Wittig rearrangement of chiral 3‐substituted 1‐propenyloxy‐1‐phenyl‐2‐propen‐1‐yl carbanions (see scheme).

     

A Rational Design of Catechol‐Based Compounds: An Experimental and Theoretical Study of Optical Properties

Finely tuned optical properties : The optical properties of substituted protected catechol derivatives can be fine‐tuned (see scheme; TBDMS=tert‐butyldimethylsilyloxy). The DFT‐calculated polarisabilities are compared with experimental data.

     

Highly Efficient Visible‐Light Plasmonic Photocatalyst Ag@AgBr

Visible improvements : Owing to the plasmon resonance of silver nanoparticles deposited on the surface of AgBr, the newly‐prepared plasmonic photocatalyst Ag§AgBr has a strong absorption in the visible region (see picture) and shows high efficiency in the photodegradation of organic pollutants under visible light.

     

Generating CuII–Oxyl/CuIII–Oxo Species from CuI–α‐Ketocarboxylate Complexes and O2: In Silico Studies on Ligand Effects and C?H‐Activation Reactivity

Theoretically speaking : The mechanistic details associated with the generation and reaction of [CuO]⁺ species from Cu^I–α‐ketocarboxylate complexes, especially with respect to modifications of the ligand supporting the copper center, were investigated (see scheme). Theoretical models were used to characterize the electronic structures of different [CuO]⁺ species and their reactivity in C? H activation and O‐atom transfer reactions.

     

Palladium‐Catalyzed Intramolecular Hydroamination of Allenes Coupled to Aerobic Alcohol Oxidation

Taking the air! A Pd^II‐catalyzed intramolecular hydroamination of allenes coupled to alcohol oxidation has been developed. This reaction is performed by using a nitrogen‐based ligand under aerobic conditions, under which the molecular oxygen is used as the terminal oxidant for the reoxidation of Pd⁰ species to complete the catalytic cycle.

     

Synthesis,Properties and Formation of (RCp)Co‐ and (RCp)Rh‐Stabilized[4.8]3Cyclacene Derivatives

Metal‐stabilized belts : A torus, 3 , consisting of three four‐ and three eight‐membered conjugated rings and stabilized by (RCp)Co‐ and (RCp)Rh‐ units, was generated by irradiation of [(RCp)Co(CO)₂] and [(RCp)Rh(C₂H₄)₂], respectively, and 1 .

     

Dual Organocatalysis: Asymmetric Allylic–Allylic Alkylation of α,α‐Dicyanoalkenes and Morita–Baylis–Hillman Carbonates

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.

     

Reversible Uptake of COS,CS2, and SO2: Ionic Liquids with O‐Alkylxanthate,O‐Alkylthiocarbonyl,and O‐Alkylsulfite Anions

CO₂‐binding organic liquids (CO₂BOLs) are mixtures of a base (typically an amidine or guanidine) and an alcohol, and have been shown to reversibly capture and release CO₂ with low reaction energies and high gravimetric CO₂ capacity. We now report the ability of such liquid blends to chemically bind and release other acid gases such as CS₂, COS, and SO₂ analogously to CO₂. These systems bind with sulfur‐containing acid gases to form colored ionic liquids with new O‐alkylxanthate, O‐alkylthiocarbonyl, and O‐alkylsulfite anions. The capture and thermal stripping of each acid gas from these systems and their applicability towards flue gas desulfurization is discussed.