Iron porphyrin catalysed light driven C–H bond amination and alkene aziridination with organic azides

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation.

An iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.     

Spatiotemporal Studies of the One-Dimensional Coordination Polymer [Fe(ebtz)2(C2H5CN)2](BF4)2: Tug of War between the Nitrile Reorientation Versus Crystal Lattice as a Tool for Tuning the Spin Crossover Properties**

Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF₄)₂⋅6 H₂O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz)₂(RCN)₂](BF₄)₂⋅nRCN (n=2 for R=CH₃ ( 1 ) and n=0 for R=C₂H₅ ( 2 ) C₃H₇ ( 3 ), C₃H₅ ( 4 ), CH₂Cl ( 5 )) exhibiting spin crossover (SCO). SCO in 1 and 3 – 5 is complete and occurs above 160 K. In 2 , it is shifted to lower temperatures and is accompanied by wide hysteresis (T_1/2^↓=78 K, T_1/2^↑=123 K) and proceeds extremely slowly. Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed a complex nature for the HS→LS transition in 2 . An initial, slow stage is associated with shrinkage of polymeric chains and with reduction of volume at 77 % (in relation to the difference between cell volumes V_HS−V_LS) whereas only 16 % of iron(II) ions change spin state. In the second stage, an abrupt SCO occurs, associated with breathing of the crystal lattice along the direction of the Fe–nitrile bonds, while the nitriles reorient. HS→LS switching triggered by light (808 nm) reveals the coupling of spin state and nitrile orientation. The importance of this coupling was confirmed by studies of [Fe(ebtz)₂(C₂H₅CN/C₃H₇CN)₂](BF₄)₂ mixed crystals ( 2 a , 2 b ), showing a shift of T_1/2 to higher values and narrowing of the hysteresis loop concomitant with an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Density functional theory (DFT) studies of models of 1 – 5 suggest a particular possibility of 2 to adopt a low (140–145°) value of its Fe-N-C(propionitrile) angle.     

Water and oil signal assignment in low-moisture mozzarella as determined by time-domain NMR T2 relaxometry

A time-domain ¹H nuclear magnetic resonance relaxometry method was elaborated for the rapid microstructural characterization of mozzarella cheese. For this purpose, there is a strong need to know how the experimentally determined T₂ relaxation time distribution can be related to specific constituents in mozzarella. In this study, a detailed investigation is offered for fresh and aged low-moisture mozzarella cheese, often applied as a pizza cheese, by application of both a conventional Carr–Purcell–Meiboom–Gill (CPMG) sequence and a free-induction decay CPMG (FID-CPMG) sequence. The relaxation behavior was further elucidated by addition of deuterium oxide and by mild heat treatment of samples. The relaxation times of water protons in mozzarella were found to range from a few microseconds to some tens of milliseconds (in aged mozzarella) or to about hundred milliseconds (in fresh mozzarella). The upper limit of the T₂ distribution can even be extended to the seconds range upon releasing water protons from the mozzarella matrix using a mild heat treatment or upon addition of deuterated water. Both stimuli also provided evidence for the absorption of water into the cheese matrix. The potential release and uptake of water demonstrated that mozzarella acts as a very dynamic system during production and storage. The detected differences in the behavior of the water fraction between fresh and aged low-moisture mozzarella might be utilized to study the influence of either production and/or storage conditions on the cheese ripening process.     

Interference effect of an upstream larger cylinder on the lock-in vibration of a flexibly mounted circular cylinder

Experiments have been carried out to investigate the flow-induced vibration response of a flexibly mounted circular cylinder located in the vicinity of a larger cylinder and subjected to cross-flow. The interfering larger cylinder was placed upstream and had a diameter twice that of the vibrating cylinder. Complex interaction was observed between the flow over the two cylinders. The vibration responses of the flexible cylinder were classified into different regimes according to the relative positions of the two cylinders. In the-side-by-side arrangement and the tandem or near-tandem arrangement, flow-induced vibrations of the flexible cylinder were greatly suppressed. In the staggered arrangement which covered a large portion of the relative cylinder positions being investigated, vibrations of the smaller cylinder were greatly amplified. The vibration response curves were also largely modified with a broadening of the lock-in resonance range. A shift of the peak reduced velocity for maximum vibration response was also found. Flow visualizations and wake velocity measurements suggested that the modifications of the vibration responses were related to the presence or absence of constant or intermittent flow through the gap region between the two cylinders. The proposed mechanisms of flow interactions and the resulting vibration response characteristics could explain previous observations on flow-induced vibrations of two equal-sized circular cylinders reported in the literature.     

Supramolecular Catalysis of the oxa-Pictet–Spengler Reaction with an Endohedrally Functionalized Self-Assembled Cage Complex

An endohedrally functionalized self-assembled Fe₄L₆ cage complex can catalyze oxa-Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size-selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size-selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.     

Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

Trifluoromethoxy (OCF₃) and difluoromethoxy (OCF₂H) groups are fluorinated structural motifs that exhibit unique physicochemical characteristics. Incorporation of these substituents into organic molecules is a highly desirable approach used in medicinal chemistry and drug discovery processes to alter the properties of a parent compound. Recently, tri‐ and difluoromethyl ethers have received increasing attention and several innovative strategies to access these valuable functional groups have been developed. The focus of this Minireview is the use of visible‐light photoredox catalysis in the synthesis of tri‐ and difluoromethyl ethers. Recent photocatalytic strategies for the formation of O?CF₃, C?OCF_3, O?CF₂H, and C?OCF₂H bonds as well as other transformations leading to the construction of OR_F groups are discussed herein.     

A Self-Assembled Cage with Endohedral Acid Groups both Catalyzes Substitution Reactions and Controls Their Molecularity

A self-assembled Fe₄L₆ cage complex internally decorated with acid functions is capable of accelerating the thioetherification of activated alcohols, ethers and amines by up to 1000-fold. No product inhibition is seen, and effective supramolecular catalysis can occur with as little as 5 % cage. The substrates are bound in the host with up to micromolar affinities, whereas the products show binding that is an order of magnitude weaker. Most importantly, the cage host alters the molecularity of the reaction: whereas the reaction catalyzed by simple acids is a unimolecular, S_N1-type substitution process, the rate of the host-mediated process is dependent on the concentration of nucleophile. The molecularity of the cage-catalyzed reaction is substrate-dependent, and can be up to bimolecular. In addition, the catalysis can be prevented by a large excess of nucleophile, where substrate inhibition dominates, and the use of tritylated anilines as substrates causes a negative feedback loop, whereby the liberated product destroys the catalyst and stops the reaction.