Facile Synthesis and Systematic Investigations of a Series of Novel Bent‐Shaped Two‐Photon Absorption Chromophores Based on Pyrimidine

Mark us bent! The synthesis, structure, and single‐ and two‐photon spectroscopic properties of a series of pyrimidine‐based (bent‐shaped) molecules are reported. These allow structure‐property relationships and guidelines for both the development and application of TPA compounds to be derived.

     

Oxindole Synthesis by Direct Coupling of C?H and C?H Centers

An sp ² /sp ³ get‐together : A novel and efficient method can be used to synthesize 3,3‐disubstitued oxindoles by the direct intramolecular oxidative coupling of an aryl C? H and a C? H center (see scheme; DMF=N,N‐dimethylformamide).

     

C?F Activation at Rhodium Boryl Complexes: Formation of 2‐Fluoroalkyl‐1,3,2‐Dioxaborolanes by Catalytic Functionalization of Hexafluoropropene

Fluorinated building blocks by C? F bond cleavage : Catalytic C? F activation reactions that give novel dioxaborolanes have been developed (see scheme). The reactions proceed at room temperature, and catalytic intermediates are presumably rhodium hydride and boryl species.

     

Fast Synthesis of Benzofluorenes by Selenium‐Mediated Carbocyclizations

When one ring is not enough : A new double cyclization of stilbene derivatives results in benzo[b]fluorenes via dihydronaphthalenes. The presence of a selenium electrophile and a Lewis acid are crucial for the formation of the C? C bonds.

     

Synthesis of the DFGH ring system of Type B Physalins: Highly Oxygenated,Cage‐Shaped Molecules

Let the dominos fall : Synthesis of the complex DFGH ring system of the title compounds has been accomplished. The approach features simple treatment of the key intermediate with a Brønsted base to afford the tetracyclic cage‐shaped target in one pot through a four‐step domino transformation (see scheme; Mc= monochloromesylate, MOM=methoxymethyl).

     

Water Splitting by Light with Osmocene as Photocatalyst

Last but not least : A simple molecular redox system is used to split water into hydrogen and oxygen photochemically. Two separate photolyses are combined to a cyclic process (see scheme). Osmocene ([Cp₂Os^II] with Cp^?=C₅H₅^?) serves as photocatalyst.

     

Bridging M?Cl Bonds with Ambiphilic Phosphine–Borane Ligands

Bridging or pendant? Palladium and rhodium complexes deriving from an ambiphilic phosphine–borane ligand are shown to adopt a bridging P→M? Cl→B coordination mode in the solid state. DFT calculations provide more insight into the Cl→B interaction and suggest the possible interconversion of the bridging and B‐pendant forms in solution.

     

An Efficient Strategy to Drive Nanoparticles into Carbon Nanotubes and the Remarkable Effect of Confinement on Their Catalytic Performance

Are you in? Bimetallic PtRu nanoparticles have been selectively confined inside or deposited outside carbon nanotubes (see picture). The confined nanoparticles display significantly higher selectivity and catalytic activity in hydrogenation reactions.

     

Sandro Gambarotta

“The biggest challenge facing chemists is being creative. When I was eighteen I wanted to be an astrophysicist…︁.” This and more about Sandro Gambarotta can be found on page 2449.

     

K. Suzuki

“My first experiment was preparation of proline‐derived chiral ligands for asymmetric alkylation. My favorite subjects at school were history and English…?.” This and more about Keisuke Suzuki can be found on page 2635.

     

Synthesis of 1,3‐Diamines Through Rhodium‐Catalyzed C?H Insertion

Schließen und öffnen : N‐Boc‐N‐alkylsulfamide sind geeignete Substrate für die Titelreaktion. Die oxidative Cyclisierung im ersten Schritt ist hoch chemoselektiv sowie stereospezifisch und diastereoselektiv. Mit neuen Verfahren zur Öffnung der dabei erhaltenen Sechsringheterocyclen werden unterschiedlich geschützte 1,3‐Diamine zugänglich (siehe Schema).

     

From Oblivion into the Limelight: Iron (Domino) Catalysis

Sleeping beauty? Is the scientific community about to kiss awake iron catalysis, a topic that has been dormant for decades? A recent study on a user‐friendly direct cross‐coupling reaction of alkyl and aryl halides constitutes an important step toward this end through the integration of two different iron‐catalyzed elementary steps into a practical one‐pot procedure.

     

N4‐Tetradentate Dicarboxyamidate/Dipyridyl Palladium Complexes as Robust Catalysts for the Heck Reaction of Deactivated Aryl Chlorides

Structurally well defined and thermally stable Pd^II complexes, derived from N4‐tetradentate dicarboxyamide/dipyridyl ligands, were evaluated as catalysts for the Heck reactions of deactivated aryl chlorides and olefins (see scheme). The concept of using an anionic carboxyamide as an ancillary ligand for palladium demonstrated here provides a new opportunity for the development of phosphine‐free transition‐metal catalysis.

     

Gold‐Catalyzed Homogeneous Oxidative Cross‐Coupling Reactions

Oxidizing gold? A gold(I)/gold(III) catalytic cycle is essential for the first oxidative cross‐coupling reaction in gold catalysis. By using Selectfluor for gold(I) oxidation, this chemistry reveals the synthetic potential of incorporating gold(I)/gold(III) catalytic cycles into contemporary gold chemistry and promises a new area of gold research by merging powerful gold catalysis and oxidative metal‐catalyzed cross‐coupling reactions.