Post‐Metallocenes in the Industrial Production of Polyolefins

Research on “post‐metallocene” polymerization catalysis ranges methodologically from fundamental mechanistic studies of polymerization reactions over catalyst design to material properties of the polyolefins prepared. A common goal of these studies is the creation of practically useful new polyolefin materials or polymerization processes. This Review gives a comprehensive overview of post‐metallocene polymerization catalysts that have been put into practice. The decisive properties for this success of a given catalyst structure are delineated.     

Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium‐Catalyzed Buchwald–Hartwig Amination

A challenging synthetic modification of PEPPSI‐type palladium pre‐catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4‐chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600).     

Ultrafast Photoswitching in a Copper‐Nitroxide‐Based Molecular Magnet

Molecular compounds with photoswitchable magnetic properties have been intensively investigated over the last decades due to their prospective applications in nanoelectronics, sensing and magnetic data storage. The family of copper‐nitroxide‐based molecular magnets represents a new promising type of photoswitchable compounds. We report the first study of these appealing systems using femtosecond optical spectroscopy. We unveil the mechanism of ultrafast (<50 fs) spin state photoswitching and establish its principal differences compared to other photoswitchable magnets. On this basis, we propose potential advantages of copper‐nitroxide‐based molecular magnets for the future design of ultrafast magnetic materials.     

Catalytic Cleavage of Ether CO Bonds by Pincer Iridium Complexes

The development of efficient catalytic methods to cleave the relatively unreactive C? O bonds of ethers remains an important challenge in catalysis. Building on our group’s recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom‐economical method for ether C? O bond cleavage.     

Iodonium Metathesis Reactions

A metathesis reaction occurs when a diaryliodonium triflate is heated with an aryl iodide, resulting in the formation of a new diaryliodonium triflate.     

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state.     

Iridium‐Catalyzed Regio‐ and Enantioselective Allylic Substitution of Silyl Dienolates Derived from Dioxinones

Reported herein is the iridium‐catalyzed regio‐ and enantioselective allylic substitution reactions of unstabilized silyl dienolates derived from dioxinones. Asymmetric allylic substitution of a variety of allylic trichloroethyl carbonates with these silyl dienolates gave γ‐allylated products selectively in 60–84 % yield and 90–98 % ee.     

A Complete Switch of the Directional Selectivity in the Annulation of 2‐Hydroxybenzaldehydes with Alkynes

Controlling reaction selectivity is an eternal pursuit for chemists working in chemical synthesis. As part of this endeavor, our group has been exploring the possibility of constructing different natural product skeletons from the same simple starting materials by using different catalytic systems. In our previous work, an isoflavanone skeleton was obtained from the annulation of a salicylaldehyde and an alkyne when a gold catalyst was employed. In this paper, it is shown that a coumarin skeleton can be efficiently obtained through an annulation reaction with the same starting materials, that is, terminal alkynes and salicylaldehydes, by simply switching to a rhodium catalyst. A plausible reaction mechanism is proposed for this new annulation based on isotopic substitution experiments.