Sterically Hindered Luminescent PtII–Phosphite Complexes for Electroluminescent Devices

Pt^II complexes with one bulky, sterically demanding, tertiary phosphite ancillary ligand and a coordinating chromophore are herein presented. The phosphite ligand, tris(2,4‐di‐tert‐butylphenyl) acts as a bidentate ligand coordinating the platinum ion through the central phosphorus atom and a cyclometalating carbon atom of one of the substituents. The two free phenoxy moieties lie above and below the coordination plane, leading to steric hindrance that avoids aggregation and provides solubility in organic solvents. The other two coordination sites on the central metal ion are occupied by a chromophoric ligand, which is responsible for the energy of the luminescent excited state. This separation of functions, on the two coordinated ligands, allows the use of a wider range of luminophores with good luminescent properties, maintaining the control of the intermolecular interactions with the non‐chromophoric ligand. Based on this approach we were able to achieve a bright deep blue emission (λ=444 nm, Φ_em=0.38) from a complex with a tailored ligand, which was then used for the fabrication of an electroluminescent device. In addition commercially available luminophores were also employed to synthesize green emitters.     

C-Triazolyl β-d-furanosides as LpxC inhibitors: stereoselective synthesis and biological evaluation

C-Triazolyl β-d-furanosides 10a–f were synthesized in a stereocontrolled way, starting from d-mannose. In the key steps of the synthesis a diastereoselective reduction of hemiketal 14 and a Cu(I) catalyzed [3+2]-cycloaddition of central building block 18 with various azides were performed. The synthesized hydroxamic acids were tested for their inhibitory activity against LpxC, a Zn²⁺-dependent deacetylase playing an important role in the biosynthesis of lipid A and therefore representing an interesting target for the development of novel antibiotics against Gram-negative bacteria. The C-triazolyl glycosides 10a–f did not exhibit antibiotic activity. However, the described synthesis is a versatile way to access C-triazolyl β-d-furanosides bearing all of their substituents at the same side of the tetrahydrofuran ring.     

Conjugate Umpolung of β,β‐Disubstituted Enals by Dual Catalysis with an N‐Heterocyclic Carbene and a Brønsted Acid: Facile Construction of Contiguous Quaternary Stereocenters

A sterically hindered homoenolate has been generated by the NHC‐catalyzed conjugate umpolung of β,β‐disubstituted enals and successfully employed in a facile stereoselective annulation with isatins. The strategy provides efficient access to spirocyclic oxindoles bearing two highly congested contiguous quaternary carbon centers. The use of a Brønsted acid cocatalyst was found to be crucial for guaranteeing both excellent reactivity and high stereoselectivity.     

Asymmetric Synthesis of Highly Substituted β‐Lactones through Oxidative Carbene Catalysis with LiCl as Cooperative Lewis Acid

The reaction of enals with β‐diketones, β‐ketoesters, and malonates bearing a β‐oxyalkyl substituent at the α‐position by oxidative NHC catalysis to provide highly substituted β‐lactones is described. Reactions occur with excellent diastereo‐ and enantioselectivity. The organo cascade comprises two C? C bond formations and one C? O bond formation. Up to four contiguous stereogenic centers including two fully substituted stereocenters are formed in the cascade.     

N‐Heterocyclic Carbene Catalyzed Formal [3+2] Annulation Reaction of Enals: An Efficient Enantioselective Access to Spiro‐Heterocycles

A highly enantioselective N‐heterocyclic carbene (NHC) catalyzed formal [3+2] annulation of α,β‐unsaturated aldehydes with azaaurones or aurone generating spiro‐heterocycles has been developed. The protocol represents a unique NHC‐activation‐based approach to access spiro‐heterocyclic derivatives bearing a quaternary stereogenic center with high optical purity (up to 95 % ee).     

A unique six-membered chelated iridium complex

The reaction of 2-(3-methylbiphenyl-2-yl)pyridine with IrCl(3).nH(2)O in the presence of water incorporates a tightly bonded CO at the iridium center; in the subsequent reaction with picolinic acid a complex revealing an unusual CH activation of a methyl group is formed.     

Formation of Thermally Robust Frustrated Lewis Pairs by Electrocyclic Ring Closure Reactions

The phosphorus/boron‐substituted hexatriene systems 6 undergo thermally induced electrocyclic ring closure to yield the cyclohexadiene‐derived P/B frustrated Lewis pairs (FLPs) 7 . Subsequent TEMPO oxidation gives the phenylene‐bridged FLPs 8 . Both systems activate dihydrogen and the thermally robust FLPs undergo carbon–carbon coupling reactions at a mesityl group upon treatment with dimethyl acetylenedicarboxylate at elevated temperatures.     

Tuning the Molecular Packing of Self-Assembled Amphiphilic PtII Complexes by Varying the Hydrophilic Side-Chain Length

Understanding the relationship between molecular design and packing modes constitutes one of the major challenges in self-assembly and is essential for the preparation of functional materials. Herein, we have achieved high precision control over the supramolecular packing of amphiphilic Pt^II complexes by systematic variation of the hydrophilic side-chain length. A novel approach of general applicability based on complementary X-ray diffraction and solid-state NMR spectroscopy has allowed us to establish a clear correlation between molecular features and supramolecular ordering. Systematically increasing the side-chain length gradually increases the steric demand and reduces the extent of aromatic interactions, thereby inducing a gradual shift in the molecular packing from parallel to a long-slipped organization. Notably, our findings highlight the necessity of advanced solid-state NMR techniques to gain structural information for supramolecular systems where single-crystal growth is not possible. Our work further demonstrates a new molecular design strategy to modulate aromatic interaction strengths and packing arrangements that could be useful for the engineering of functional materials based on Pt^II and aromatic molecules.     

Highly Enantioselective Intramolecular 1,3‐Dipolar Cycloaddition: A Route to Piperidino‐Pyrrolizidines

Enantioselective catalytic intermolecular 1,3‐dipolar cycloadditions are powerful methods for the synthesis of heterocycles. In contrast, intramolecular enantioselective 1,3‐dipolar cycloadditions are virtually unexplored. A highly enantioselective synthesis of natural‐product‐inspired pyrrolidino‐piperidines by means of an intramolecular 1,3‐dipolar cycloaddition with azomethine ylides is now reported. The method has a wide scope and yields the desired cycloadducts with four tertiary stereogenic centers with up to 99 % ee. Combining the enantioselective catalytic intramolecular 1,3‐dipolar cycloaddition with a subsequent diastereoselective intermolecular 1,3‐dipolar cycloaddition yielded complex piperidino‐pyrrolizidines with very high stereoselectivity in a one‐pot tandem reaction.