Palladium-Catalyzed Enantioselective Alkenylation of Enelactams Using a Relay Heck Strategy

In this report, a palladium-catalyzed redox-relay Heck process to access optically active alkenylated α,β-unsaturated lactams is described. Under mild reaction conditions, electron-deficient alkenyl triflates and electron-rich alkenyl iodonium salts undergo enantioselective and site-selective coupling with enelactams to deliver the products in high yields and excellent enantioselectivities. Furthermore, the products allow facile access to natural products such as (+)-calvine and (+)-2-epicalvine in addition to the bioactive molecule aza-goniothalamin.     

Enzyme Promiscuity as a Remedy for the Common Problems with Knoevenagel Condensation

A new protocol based on lipase-catalyzed tandem reaction toward α,β-enones/enoesters is presented. For the synthesis of the desired products the tandem process based on enzyme-catalyzed hydrolysis and Knoevenagel reaction starting from enol acetates and aldehyde is developed. The relevant impact of the reaction conditions including organic solvent, enzyme type, and temperature on the course of the reaction was revealed. It was shown that controllable release of the active methylene compound from the corresponding enol carboxylate ensured by enzymatic reaction diminishes significantly the formation of the unwanted co-products. Furthermore, this protocol was extended by including a second tandem chemoenzymatic transformation engaging various aldehyde precursors. After a careful optimization of the reaction conditions, the target products were obtained with yields up to 86 % and with excellent E/Z-selectivity.     

Phosphahelicenes with (Thio)Phosphinic Acid and Ester Functions by the Oxidative Photocyclisation Approach

Phosphahelicenes with thiophosphinic acid and ester functions have been obtained by the oxidative photocyclisation of olefins bearing both a benzophenanthrene and a benzophosphole unit. When the method has been extended to olefins bearing a partially saturated benzophospholene unit, a divergent regioselectivity of the photocyclisation step has been observed, leading to new helicenes in which the phosphorus function is located on the external rim of the helical backbone. The observed regioselectivity correlates well with the free-valence numbers of the atoms involved in the photocyclisation reaction (DFT calculations).     

Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen

A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals.     

Diphospha-Ureas from the Phosphaketene Ph3GePCO

The phosphaketene Ph₃GePCO is shown to react with the phosphide KP(tBu)₂ to generate the anion [Ph₃GePC(O)P(tBu)₂]⁻ 1 . This species reacts with CH₃I or ClGePh₃ to give the dissymmetric diphospha-ureas (tBu)₂PC(O)P(GePh₃)(CH₃) 2 and (Ph₃Ge)₂PC(O)P(tBu)₂ 3 respectively. Sequential treatment of 2 with a base and CH₃I affords a route to (tBu)₂PC(O)P(CH₃)₂ 5 . These species are products of the first modular diphospha-urea synthesis. The subsequent thermal and photochemical reactivity of these species was also probed and described.     

Recent Advances in Zeolite-like Cluster Organic Frameworks

During the past decade, research on the design and synthesis of zeolite-like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed.     

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

An interesting phenomenon is reported when uranyl peroxide nanoclusters U₆₀ (Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n, m≈20 and n≈310) interact with a small number of cationic surfactant molecules. Cationic surfactant molecules do not distribute evenly around the U₆₀ clusters during the interaction as expected. Instead, a small fraction of U₆₀ clusters attract almost all the surfactant molecules, leading to the self-assembly into supramolecular structures by using surfactant–U₆₀ complexes as building locks, and later further aggregate and precipitate based on hydrophobic interaction, whereas the rest of the clusters remained unbounded soluble macroions in bulk dispersion. This phenomenon nicely demonstrates a unique feature of macroion solutions. Considering that Debye–Hückel approximation is no longer valid in such solutions, the competition between the local electrostatic interaction and hydrophobic interaction becomes important to regulate the solution behaviors of macroions.     

Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C−H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τ_P) of 1.1 s and a phosphorescence quantum yield (Φ_P) of 1.2 %, whereas the bromine-substituted derivative exhibits τ_P of 0.15 s with a Φ_P of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

Synthetic Studies on Spirolides A and B: Formation of the Upper Carbon Framework Based on a Lewis Acid Template-Catalyzed Diels–Alder Reaction

The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate.