Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, p-stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bioand materials science. In the last few years, [2.2]paracyclophane chemistry has progressed tremendously, enabling the fine-tuning of ist structural and functional properties. This Minireview highlights the most important recent synthetic developments in the selective functionalization of PCP that govern distinct features of planar chirality as well as chiroptical and optoelectronic properties. Special focus is given to the function-inspired design of [2.2]paracyclophane-based pstacked conjugated materials by transition-metal-catalyzed crosscoupling reactions. Current synthetic challenges, limitations, as well as future research directions and new avenues for advancing cyclophane chemistry are also summarized

Controlling Regioselectivity in Palladium-Catalyzed C-H Activation/Aryl-Aryl Coupling of 4-Phenylamino[2.2]paracyclophane

Selective activation/functionalization of C-H bonds has emerged as an atom- and step-economical process at the forefront of modern synthetic chemistry. This work reports palladium-catalyzed exclusivelypara-selective C-H activation/aryl-aryl bond formation with a preference overN-arylation under the Buchwald-Hartwig amination reaction of 4-phenylamino[2.2]paracyclophane. This innovative synthetic strategy allows a facile preparation of [2.2]paracyclophane derivatives featuring disparatepara-substitutions at C-4 and C-7 positions in a highly selective manner, gives access to a series of potential candidates for [2.2]paracyclophane-derived new planar chiral ligands. The unprecedented behavior in reactivity and preferential selectivity of C-C coupling over C-N bond formation via C-H activation is unique to the [2.2]paracyclophane scaffold compared to the non-cyclophane analogue under the same reaction conditions. Selective C-H activation/aryl-aryl bond formation and sequential C-N coupling product formation is evidenced unambiguously by X-ray crystallography.Peer reviewe

Assembly of Molecular Building Blocks into Integrated Complex Functional Molecular Systems: Structuring Matter Made to Order

Function-inspired design of molecular building blocks for their assembly into complex systems has been an objective in engineering nanostructures and materials modulation at nanoscale. This article summarizes recent research and inspiring progress in the design/synthesis of various custom-made chiral, switchable, and highly responsive molecular building blocks for the construction of diverse covalent/noncovalent assemblies with tailored topologies, properties, and functions. Illustrating the judicious selection of building blocks, orthogonal functionalities, and innate physical/chemical properties that bring diversity and complex functions once reticulated into materials, special focus is given to their assembly into porous crystalline networks such as metal/covalent–organic frameworks (MOFs/COFs), surface-mounted frameworks (SURMOFs), metal–organic cages/rings (MOCs), cross-linked polymer gels, porous organic polymers (POPs), and related architectures that find diverse applications in life science and various other functional materials. Smart and stimuli-responsive or dynamic building blocks, once embedded into materials, can be remotely modulated by external stimuli (light, electrons, chemicals, or mechanical forces) for controlling the structure and properties, thus being applicable for dynamic photochemical and mechanochemical control in constructing new forms of matter made to order. Then, an overview of current challenges, limitations, as well as future research directions and opportunities in this field, are discussed

The Staudinger Ligation

While the Staudinger reaction has first been described a hundred years ago in 1919, the ligation reaction became one of the most important and efficient bioconjugation techniques in the 1990s and this century. It holds the crucial characteristics for bioorthogonal chemistry: biocompatibility, selectivity, and a rapid and high-yielding turnover for a wide variety of applications. In the past years, it has been used especially in chemical biology for peptide/protein synthesis, posttranslational modifications, and DNA labeling. Furthermore, it can be used for cell-surface engineering, development of microarrays, and drug delivery systems. However, it is also possible to use the reaction in synthetic chemistry for general formation of amide bonds. In this review, the three major types, traceless and nontraceless Staudinger Ligation as well as the Staudinger phosphite reaction, are described in detail. We will further illustrate each reaction mechanism and describe characteristic substrates, intermediates, and products. In addition, not only its advantages but also stereochemical aspects, scope, and limitations, in particular side reactions, are discussed. Finally, the method is compared to other bioorthogonal labeling methods

Ruthenium-catalyzed C-H activation of thioxanthones

Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented

Synthesis of bis-oxathiaaza[3.3.3]propellanes via nucleophilic addition of (1,ω-alkanediyl)bis(N′-organylthioureas) on dicyanomethylene-1,3-indanedione

A concise and efficient route for synthesis of bis-oxathiaaza[3.3.3]propellanes by reaction of N,N,-N″-(1,ω-alkanediyl)bis-(N″-organylthioureas) with (1,3-dioxo-2,3-dihydro-1H-inden-2- ylidene)propanedinitrile is reported. The structures of the products have been confirmed by using NMR as well as single crystal X-ray analysis for one product. A plausible mechanism for formation of the products is presented.Peer reviewe

Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal-organic frameworks based on DUT-5

Functionalized 4,4′-biphenyldicarboxylic acid molecules with additional amine, alkyne, azide or nitro groups were prepared and applied in the synthesis of novel metal-organic frameworks and mixed-linker metal-organic frameworks isoreticular to DUT-5. The properties of the frameworks could be tuned by varying the number of functional groups in the materials and the amine groups were employed in post-synthetic modification reactions without changing the framework structure or significantly decreasing the porosity of the materials. © The Royal Society of Chemistry 2015

Post-synthetic Modification of DUT-5-based Metal Organic Frameworks for the Generation of Single-site Catalysts and their Application in Selective Epoxidation Reactions

New single‐site catalysts based on mixed‐linker metal‐organic frameworks with DUT‐5 structure, which contain immobilized Co2+, Mn2+ and Mn3+ complexes, have successfully been synthesized via post‐synthetic modification. 2,2’‐Bipyridine‐5,5’‐dicarboxylate linkers were directly metalated, while 2‐amino‐4,4’‐biphenyldicarboxylate linkers were post‐synthetically modified by their conversion to Schiff‐base ligands and a subsequent immobilization of the metal complexes. The resulting materials were used as catalysts in the selective epoxidation of trans‐stilbene and the activities and selectivities of the different catalysts were compared. The influence of various reaction parameters on conversion, yield and selectivity were investigated. Very low catalyst amounts of 0.02 mol % were sufficient to obtain a high conversion of trans‐stilbene using molecular oxygen from air as the oxidant. For cobalt‐containing MOF catalysts, conversions up to 90 % were observed and, thus, they were more active than their manganese‐containing counterparts. Recycling experiments and hot filtration tests proved that the reactions were mainly catalyzed via heterogeneous pathways

Thiol-yne crosslinked triarylamine hole transport layers for solution-processable organic light-emitting diodes

Triarylamine derivatives are widely used for hole transport in organic optoelectronic devices, but their excellent solubility in many common solvents limits their use for multi-layer device fabrication from solution. In this work, a novel process to the formation of conjugated triarylamine polymer thin-film networks by crosslinking of thiol-substituted and alkyne-substituted triarylamines is investigated. After deposition of the monomer blend and crosslinking under UV exposure, an insoluble thiol-yne polymer network is formed. The applicability of the thiol-yne polymer network as hole-transport layers is exemplified on organic light-emitting diodes. Its implementation reduces the device degradation as compared to OLEDs comprising hole-transport layers from PEDOT:PSS