Structure elucidation of cyclohexene (9Z)-octadec-9-enyl ethers isolated from the leaves of Uvaria cherrevensis (Annonaceae)

The phytochemical investigation of the leaf extract of Uvaria cherrevensis (Annonaceae) yielded three new cyclohexene (9Z)-octadec-9-enyl ethers, cherrevenols M-O (1–3), and a known fatty ester derivative (4). The structures of the isolated compounds were elucidated by spectroscopic and computer-aided molecular modelling methods. Ozone Induced Dissociation (OzID) mass spectrometry was employed to determine the C-9 position of the side chain olefinic double bonds, while ¹³C NMR spectroscopy indicated their (Z)-configurations. All isolated compounds were evaluated for their antimalarial and cytotoxic activities; all were inactive.     

An N‐Heterocyclic Carbene with a Saturated Backbone and Spatially‐Defined Steric Impact

The synthesis and coordination chemistry of a saturated analogue of a “bulky‐yet‐flexible” N‐heterocyclic carbene (NHC) ligand are described. “SIPaul” is a 4,5‐dihydroimidazol‐2‐ylidene ligand with unsymmetrical aryl N‐substituents, and is one of the growing class of “bulky‐yet‐flexible” NHCs that are sufficiently bulky to stabilize catalytic intermediates, but sufficiently flexible that they do not inhibit productive chemistry at the central metal atom. Here, the synthesis of SIPaul.HCl and its complexes with copper, silver, iridium, palladium, and nickel, and its selenourea, are reported. The steric impact of the ligand is quantified using percent buried volume (% V_bur), whereas the electronic properties are probed and quantified using the Tolman Electronic Parameter (TEP) and δ_Se of the corresponding selenourea. This work shows that despite the often very different performance of saturated versus unsaturated carbenes in catalysis, the effect of backbone saturation on measurable properties is very small.     

Rapid Assembly of Saturated Nitrogen Heterocycles in One‐Pot: Diazo‐Heterocycle “Stitching” by N–H Insertion and Cyclization

Methods that provide rapid access to new heterocyclic structures in biologically relevant chemical space provide important opportunities in drug discovery. Here, a strategy is described for the preparation of 2,2‐disubstituted azetidines, pyrrolidines, piperidines, and azepanes bearing ester and diverse aryl substituents. A one‐pot rhodium catalyzed N–H insertion and cyclization sequence uses diazo compounds to stitch together linear 1,m‐haloamines (m=2–5) to rapidly assemble 4 ‐, 5 ‐, 6 ‐, and 7 ‐membered saturated nitrogen heterocycles in excellent yields. Over fifty examples are demonstrated, including examples with diazo compounds derived from biologically active compounds. The products can be functionalized to afford α,α‐disubstituted amino acids and applied to fragment synthesis.     

Aryl Sulfonium Salts for Site‐Selective Late‐Stage Trifluoromethylation

Incorporation of the CF₃ group into arenes has found increasing importance in drug discovery. Herein, we report the first photoredox‐catalyzed cross‐coupling of aryl thianthrenium salts with a copper‐based trifluoromethyl reagent, which enables a site‐selective late‐stage trifluoromethylation of arenes. The reaction proceeds with broad functional group tolerance, even for complex small molecules on gram scale. The method was further extended to produce pentafluoroethylated derivatives.     

Preparation of Polyfunctional Arylzinc Organometallics in Toluene by Halogen/Zinc Exchange Reactions

A wide range of polyfunctional diaryl‐ and diheteroarylzinc species were prepared in toluene within 10 min to 5 h through an I/Zn or Br/Zn exchange reaction using bimetallic reagents of the general formula R′₂Zn?2 LiOR (R′=sBu, tBu, pTol). Highly sensitive functional groups, such as a triazine, a ketone, an aldehyde, or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of a plethora of functionalized (hetero)arenes after quenching with various electrophiles. Insight into the constitution and reactivity of these bimetallic mixtures revealed the formation of highly active lithium diorganodialkoxyzincates of type [R′₂Zn(OR)₂Li₂].     

Investigation of molecular weight effects of polystyrene in ToF-SIMS using C60 and Au primary ion beams

In secondary ion mass spectrometry, polyatomic primary ion sources are known to enhance yields from many surfaces including polymers. In order to understand the fundamental causes for these increases, the enhancement as a function of material type and molecular weight needs to be delineated. In this article, we report results from a systematic investigation of polymeric films of polystyrene (PS) with varying molecular weights to examine the influence of the primary ion beam on the secondary ion yields in time of flight secondary ion mass spectrometry (ToF-SIMS). The masses of the polymers investigated ranged from 1000 to 20,000 Da, or from about n = 10 to 200 where n indicates the number of polymeric units in a polymer chain. The polymers had a narrow molecular weight range (PDI < 1.07). The multilayer polymeric films (10-30 nm) characterized by AFM were prepared by spin-casting onto silicon substrates and were analyzed using Au⁺ and C₆₀⁺ primary ion beams. The analysis with the two beams provided a useful comparison between atomic and polyatomic primary ion sources. Information gathered from this study provides insight into the role of molecular weight on the observed yield enhancement from polyatomic ion sources.     

Cosmology with weak lensing surveys

Weak gravitational lensing is responsible for the shearing and magnification of the images of high-redshift sources due to the presence of intervening matter. The distortions are due to fluctuations in the gravitational potential, and are directly related to the distribution of matter and to the geometry and dynamics of the Universe. As a consequence, weak gravitational lensing offers unique possibilities for probing the Dark Matter and Dark Energy in the Universe. In this review, we summarise the theoretical and observational state of the subject, focussing on the statistical aspects of weak lensing, and consider the prospects for weak lensing surveys in the future.     

Reduction of turbulent boundary layer induced interior noise through active impedance control

The use of a single actuator tuned to an optimum impedance to control the sound power radiated from a turbulent boundary layer (TBL) excited aircraft panel into the aircraft interior is examined. An approach to calculating the optimum impedance is defined and the limitations on the reduction in radiated power by a single actuator tuned to that impedance are examined. It is shown that there are too many degrees of freedom in the TBL and in the radiation modes of the panel to allow a single actuator to control the radiated power. However, if the panel modes are lightly damped and well separated in frequency, significant reductions are possible. The implementation of a controller that presents a desired impedance to a structure is demonstrated in a laboratory experiment, in which the structure is a mass. The performance of such a controller on an aircraft panel is shown to be effective, if the actuator impedance is similar to but not the same as the desired impedance, provided the panel resonances are well separated in frequency and lightly damped.     

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

A method for the construction of boron‐substituted quaternary carbons or diarylquaternary carbons by arylboration of highly substituted alkenylarenes is presented. A wide range of alkenes and arylbromides can participate in this reaction thus allowing for a diverse assortment of products to be prepared. In addition, a solvent dependent regiodivergent arylboration of 1,2‐disubstituted alkenylarenes is presented, thus greatly increasing the scope of products that can be accessed.