Highly insulating alkane rings with destructive σ-interference

Science China Chemistry - Destructive quantum interference (DQI) provides a unique approach to controlling the leakage current in the OFF state of molecular devices. However, the DQI in...     

Synthetic studies towards the penicisulfuranols: Synthesis of an advanced spirocyclic diketopiperazine intermediate

The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine.     

Palladium-Catalyzed Hydroaminocarbonylation of Olefins with Aliphatic Amines without Additives

Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct-1-ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N-nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo-, regio- and enantioselectivities was also studied. Plausible explanation was given for the additive-free hydroaminocarbonylation reaction.     

Development of Effective Skin Cancer Treatment and Prevention in Xeroderma Pigmentosum

Xeroderma pigmentosum (XP) is a rare, recessively transmitted genetic disease characterized by increasingly marked dyspigmentation and xerosis (dryness) of sun‐exposed tissues, especially skin. Skin cancers characteristically develop in sun‐exposed sites at very much earlier ages than in the general population; these are often multiple and hundreds or even thousands may develop. Eight complementation groups have been identified. Seven groups, XP‐A…G, are associated with defective genes encoding proteins involved in the nucleotide excision DNA repair (NER) pathway that recognizes and excises mutagenic changes induced in DNA by sunlight; the eighth group, XP‐V, is associated with defective translesion synthesis (TLS) bypassing such alterations. The dyspigmentation, xerosis and eventually carcinogenesis in XP patients appear to be due to their cells’ failure to respond properly to these mutagenic DNA alterations, leading to mutations in skin cells. A subset of cases, especially those in some complementation groups, may develop neurological degeneration, which may be severe. However, in most XP patients, in the past the multiple skin cancers have led to death at an early age due to either metastases or sepsis. Using either topical 5‐fluorouracil or imiquimod, we have developed a protocol that effectively prevents most skin cancer development in XP patients.     

Access to Nitriles from Aldehydes Mediated by an Oxoammonium Salt

A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl‐imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant.     

Aeroacoustical coupling in a ducted shallow cavity and fluid/structure effects on a steam line

A pure tone phenomenon has been observed at 460 Hz in a piping steam line. The acoustical energy has been identified to be generated in an open gate valve and to be of cavity noise type. This energy is then transmitted to the main pipe by fluid/structure coupling. The objectives here are to display the mechanism of the flow acoustic coupling in the cavity and in the duct through an aeroacoustical analysis and to understand the way of energy transfer from the fluid to the main pipe through a vibroacoustical analysis. Concerning the first objective, an experimental study by means of 2/7 scale models in air is analysed by means of numerical flow simulation. The flow acoustic phenomena are modelled by computing the Euler equations. Two different computations are carried out: in the first one, a pure Euler modelling is used, in the second one, a boundary layer obtained from experimental data is introduced in the computation in order to have a realistic flow profile upstream the cavity. The boundary layer flow profile appears to be essential to recover the experimentally observed coupling between the shear-layer instability and the acoustical transverse mode of the pipe. The numerical results confirm that the second aerodynamic mode is responsible for the oscillation. While the predicted frequency agrees about 1% with the scale model experiments, the predicted amplitude is approximately 15 dB too low. For the second objective, fluid/structure coupling in the main pipe is studied using two fully coupled methods. The first method consists in a modal analysis of the line using a fluid–structure finite element model. The second one is based on the analysis of dispersion diagrams derived from the local equations of cylindrical shells filled with fluid. The way of energy transfer in transverse acoustical waves coupled with flexion-ovalization deformations of the pipe is highlighted using both methods. The dispersion diagrams allow a fast and accurate analysis. The modal analysis using a finite-element model may complete the first one with quantitative data. The link between the fluid/acoustic and the fluid/structure analysis is then the excitation of the transverse acoustical mode of the duct.     

The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes

An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.     

On the Strategy of NMR Spectral Analysis. The 1H-NMR Spectrum of Amphetamine

The successive steps of the computer analysis of a NMR spectrum are examined. Better results can be obtained by direct simulation of tentative model spectra. As an example the ¹H-NMR spectrum of amphetamine is analysed.     

Reaction of Red Phosphorus and Phosphine with Aryl(Hetaryl)Ethenes and -Ethynes

Abstract

Nucleophilic addition of phosphide anions generated from phosphorus red or phosphine to ethenes and ethynes in the presence of super bases to afford organylphosphines and -oxides has been performed.