Stereodivergent Anion Binding Catalysis with Molecular Motors.

A photoresponsive chiral catalyst based on an oligotriazole-functionalized unidirectional molecular motor has been developed for stereodivergent anion binding catalysis. The motor function controls the helical chirality of supramolecular assemblies with chloride anions, which by means of chirality transfer enables the enantioselective addition of a silyl ketene acetal nucleophile to oxocarbenium cations. Reversal of stereoselectivity (up to 142 % Δee) was achieved through rotation of the motor core induced by photochemical and thermal isomerization steps.

From Palladium to Gold Catalysis for the Synthesis of Crushed Fullerenes and Acenes.

The quest for organic materials with improved optoelectronic properties has stimulated the development of new strategies for the preparation of polycyclic aromatic hydrocarbons. Within this context, transition metal catalysis offers unparalleled opportunities for the assembly of complex molecular architectures. The palladium-catalyzed direct C-H arylation provides straight access to biaryls without the need of prefunctionalization at the nucleophilic site, which is attractive from the perspective of the synthesis of polyarenes.

On-surface synthesis of heptacene on Ag(001) from brominated and non-brominated tetrahydroheptacene precursors.

Achieving the Ag(001)-supported synthesis of heptacene from two related reactants reveals the effect of the presence of Br atoms on the reaction process. The properties of reactants, intermediates and end-products are further characterized by scanning tunneling microscopy and spectroscopy.

Cation-Modulated Rotary Speed in a Light-Driven Crown Ether Functionalized Molecular Motor.

The design and synthesis of an overcrowded-alkene based molecular motor featuring a crown ether integrated in its stator structure has been accomplished. The photostationary state ratios and rotational speed of this motor can be modulated by cation coordination to the crown ether moiety, which can be reversed upon the addition of a competing chelating agent, thus achieving a dynamic control over the rotational behavior of the motor.

Ruthenium-Catalyzed Peri- and Ortho-Alkynylation with Bromoalkynes via Insertion and Elimination.

The alkynylation of naphthols takes place with total regiocontrol at the peri position of the hydroxyl group in the presence of [RuCl(p-cymene)] as the catalyst. This reaction features high functional group tolerance. The related ortho-alkynylation of benzoic acids proceeds under similar conditions and also shows wide functional group tolerance.

Nonacene Generated by On-Surface Dehydrogenation.

The on-surface synthesis of nonacene has been accomplished by dehydrogenation of an air-stable partially saturated precursor, which could be aromatized by using a combined scanning tunneling and atomic force microscope as well as by on-surface annealing. This transformation allowed the in-detail analysis of the electronic properties of nonacene molecules physisorbed on Au(111) by scanning tunneling spectroscopy measurements. The spatial mapping of molecular orbitals was corroborated by density functional theory calculations.

Synthesis of a Crushed Fullerene C60H24 through Sixfold Palladium-Catalyzed Arylation.

The synthesis of a new -symmetric crushed fullerene CH () has been accomplished in three steps from truxene through sixfold palladium-catalyzed intramolecular arylation of a -trialkylated truxene precursor. Laser irradiation of induces cyclodehydrogenation processes that result in the formation of C, as detected by LDI-MS.

Ready Access to the Echinopines Skeleton via Gold(I)-Catalyzed Alkoxycyclizations of Enynes.

The [3,5,5,7] tetracyclic skeleton of echinopines has been stereoselectively accessed through a gold(I)-catalyzed alkoxycyclization of cyclopropyl-tethered 1,6-enynes. The key bicyclo[4.2.

Gold-Catalyzed Reactions via Cyclopropyl Gold Carbene-like Intermediates.

Cycloisomerizations of 1,n-enynes catalyzed by gold(I) proceed via electrophilic species with a highly distorted cyclopropyl gold(I) carbene-like structure, which can react with different nucleophiles to form a wide variety of products by attack at the cyclopropane or the carbene carbons. Particularly important are reactions in which the gold(I) carbene reacts with alkenes to form cyclopropanes either intra- or intermolecularly. In the absence of nucleophiles, 1,n-enynes lead to a variety of cycloisomerized products including those resulting from skeletal rearrangements.

Tetrabenzocircumpyrene: a nanographene fragment with an embedded peripentacene core.

A new disc-shaped highly symmetric C54H20 nanographene fragment, tetrabenzocircumpyrene, has been synthesized and characterized by scanning tunnelling microscopy, demonstrating the potential of this technique for identifying highly insoluble graphenic molecules.