A review of the polycyclization reaction of the C35 polyprenoid by squalene‐hopene cyclase: Surprisingly, our results completely disagree with a previous publication in which it was reported that a hexacyclic skeleton was constructed as the single product. In our work many tri‐ and tetracyclic scaffolds were isolated, but no penta‐ or hexacycles. The reasons for the different results and the mechanism of the polycyclization reaction are discussed (see figure).
One Heck of a reaction : Treatment of arylboronic acids or aryltrifluoroborates with vinyl acetate by using a palladium(II) catalyst gives the corresponding styrenes (see scheme). No palladium reoxidant is needed and the vinylation is performed under non‐inert conditions
Osmabenzenes can be easily synthesized from two η2‐coordinated olefin osmacycles in the presence of benzonitrile by means of facile hydrogen‐transfer conversions (see graphic). Mechanisms for the formation of osmabenzenes are proposed based on DFT calculations.
Dramatic rate enhancement of reductive elimination of [Ar‐Pd‐C] was observed in the presence of a phosphine/electron‐deficient olefin ligand. Through systematic kinetic investigations of the Negishi coupling of ethyl 2‐iodobenzoate with alkylzinc chlorides (see scheme), the rate constants for reductive elimination of [Ar‐Pd‐C] were determined to be greater than 0.3 s?1, which is about four or five orders of magnitude greater than values reported previously.
The oriented attachment (OA) mechanism has been investigated as an important process in the formation of anisotropic nanostructures such as depicted. The results showed that the control of a desired phase in this system may be attained by the control of OA mechanism through pH value, obtaining several morphologies.
Finding a clear route to new structures : The design of an adaptable time warping (ATW) methodology (see figure) for automatically, quickly, and reliably deciphering X‐ray diffraction patterns is described.
Sly silyl caught in the act : Protonation of a mesitylene ring by the strongly acidic arenium carborane [CH3C6H6]‐ [CHB11Me5Br6] initiates a cascade reaction that results in a stable β‐silyl allyl cation (see picture, H yellow, C blue, silyl allyl group red). Remarkably, the driving force in the reaction suffices to disrupt a stable aromatic ring in favor of a cationic reactive intermediate.
Supramolecular chirality and liquid crystalline OFET : Achiral end‐capped oligothiophenes can be tuned to exhibit supramolecular chirality with unique striped textures showing distinct circular dichroism signals as well as a highly ordered SmE phase that leads to high hole carrier mobility.
