Copper-catalyzed functionalization of enynes

The copper-catalyzed functionalization of enyne derivatives has recently emerged as a powerful approach in contemporary synthesis. Enynes are versatile and readily accessible substrates that can undergo a variety of reactions to yield densely functionalized, enantioenriched products. In this perspective, we review copper-catalyzed transformations of enynes, such as boro- and hydrofunctionalizations, copper-mediated radical difunctionalizations, and cyclizations. Particular attention is given to the regiodivergent functionalization of 1,3-enynes, and the current mechanistic understanding of such processes.

The copper-catalyzed functionalization of enynes is a powerful approach to yield densely functionalized products. This review covers various transformations, such as boro- and hydrofunctionalizations, copper-mediated radical difunctionalizations, and cyclizations.     

Transition Metal Free Cycloamination of Prenyl Carbamates and Ureas Promoted by Aryldiazonium Salts

Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox‐neutral azocycloamination. In general, N‐aryl O‐prenyl carbamates cyclize in a photocatalytic reaction with visible light and an organic dye. With electron‐deficient diazonium salts, electronic matching with an electron‐rich N‐aryl substituent results in a reaction proceeding in the ground state, without either light or photocatalyst. Cyclic voltammetry suggests that this radical reaction is initiated by hydrogen‐atom abstraction mediated by an aryl radical, followed by a radical addition cascade and proton‐coupled hole propagation. The reaction proceeds at room temperature in short reaction times, and a range of functional groups is tolerated.     

Atroposelective arylation of biaryls by C-H activation

Axial chirality of biaryls is found in natural products, bioactive molecules, ligands and catalysts and their synthesis is therefore highly appealing. Thus, the atroposelective palladium-catalyzed C-H functionalization of chiral biaryl sulfoxides was extended to a direct arylation reaction, affording ortho-terphenyls bearing one atropisomeric axis. The high stereoselectivities, good yields and operational simplicity, along with the traceless character of the sulfoxide moiety allows access to a wide range of optically active o-terphenyls.     

Die Verwendung der Papierchromatographie zur Aluminiumbestimmung in Mineralw?ssern

Zusammenfassung Mittels aufsteigender Papierchromatographie sind durch Abtrennung von anderen Steffen der qualitative Nachweis sowie die halbquantitative und quantitative Bestimmung geringer Aluminiummengen im Mineralwasser möglich. Die quantitative Bestimmung erfordert vor der papierchromatographischen Entwicklung eine entsprechende Aufarbeitung der Wasserproben. Die Aluminiummengen auf den Chromatogrammen werden mit verdünnter Salzsäure ausgewaschen und im lichtelektrischen Colorimeter quantitativ mit Aluminonlösung ermittelt.Frl. Hannelore Merten möchte ich auch an dieser Stelle für ihre unermüdliche Mitarbeit danken.     

Uncertainty budget for determinations of mean isomer shift from Mössbauer spectra

The magnetite/maghemite content within iron oxide nanoparticles can be determined using the mean isomer shift (\(\overline {\delta }\)). However, accurate characterisation of the composition is limited by the uncertainty associated with \(\overline {\delta }\). We have identified four independent sources of uncertainty and developed a quantitative expression for the uncertainty budget. Sources of uncertainty are categorised as follows: that from the fitting of the Mössbauer spectrum (σ _fit), that of the calibration of the α-Fe reference spectrum (σ _cal), thermal corrections to the spectrum due to second order Doppler shift (SODS) (σ _Δδ ) and other experimental errors (σ _err). Each contribution is discussed in detail using ⁵⁷Fe Mössbauer spectra obtained from an iron oxide nanoparticle system at temperatures between 16 K and 295 K on different spectrometers in two different laboratories.     

Hydrogen encapsulation in a silicon clathrate type I structure: Na5.5(H2)2.15Si46: synthesis and characterization

A hydrogen-encapsulated inorganic clathrate, which is stable at ambient temperature and pressure, has been prepared in high yield. Na5.5(H2)2.15Si46 is a sodium-deficient, hydrogen-encapsulated, type I silicon clathrate. It was prepared by the reaction between NaSi and NH4Br under dynamic vacuum at 300 degrees C. The Rietveld refinement of the powder X-ray diffraction data is consistent with the clathrate type I structure. The type I clathrate structure has two types of cages where the guest species, in this case Na and H2, can reside: a large cage composed of 24 Si, in which the guest resides in the 6d crystallographic position, and a smaller one composed of 20 Si, in which the guest occupies the 2a position. Solid-state 23Na, 1H, and 29Si MAS NMR confirmed the presence of both sodium and hydrogen in the clathrate cages. 23Na NMR shows that sodium completely fills the small cage and is deficient in the larger cage. The 1H NMR spectrum shows a pattern consistent with mobile hydrogen in the large cage. 29Si NMR spectrum is consistent with phase pure type I clathrate framework. Elemental analysis is consistent with the stoichiometry Na5.5(H2.15)2Si46. The sodium occupancy was also examined using spherical aberration (Cs) corrected scanning transmission electron microscopy (STEM). The high-angle annular dark-field (HAADF) STEM experimental and simulated images indicated that the Na occupancy of the large cage, 6d sites, is less than 2/3, consistent with the NMR and elemental analysis.     

The binaural performance of a cross-talk cancellation system with matched or mismatched setup and playback acoustics

Cross-talk cancellation is a method for synthesizing virtual auditory space using loudspeakers. One implementation is the "Optimal Source Distribution" technique [T. Takeuchi and P. Nelson, J. Acoust. Soc. Am. 112, 2786-2797 (2002)], in which the audio bandwidth is split across three pairs of loudspeakers, placed at azimuths of +/-90 degrees, +/-15 degrees, and +/-3 degrees, conveying low, mid, and high frequencies, respectively. A computational simulation of this system was developed and verified against measurements made on an acoustic system using a manikin. Both the acoustic system and the simulation gave a wideband average cancellation of almost 25 dB. The simulation showed that when there was a mismatch between the head-related transfer functions used to set up the system and those of the final listener, the cancellation was reduced to an average of 13 dB. Moreover, in this case the binaural interaural time differences and interaural level differences delivered by the simulation of the optimal source distribution (OSD) system often differed from the target values. It is concluded that only when the OSD system is set up with "matched" head-related transfer functions can it deliver accurate binaural cues.     

Solvation free energies calculated using the GB/SA model: Sensitivity of results on charge sets,protocols, and force fields

The sensitivity of aqueous solvation free energies (SFEs), estimated using the GB/SA continuum solvent model, on charge sets, protocols, and force fields, was studied. Simple energy calculations using the GB/SA solvent model were performed on 11 monofunctional organic compounds. Results indicate that calculated SFEs are strongly dependent on the charge sets. Charges derived from electrostatic potential fitting to high level ab initio wave functions using the CHELPG procedure and “class IV” charges from AM1/CM1a or PM3/CM1p calculations yielded better results than the corresponding Mulliken charges. Calculated SFEs were similar to MC/FEP energies obtained in the presence of explicit TIP4P water. Further improvements were obtained by using GVB/6-31G** and MP2/6-31+G** (CHELPG) charge sets that included correlation effects. SFEs calculated using charge sets assigned by the OPLSA* force field gave the best results of all standard force fields (MM2*, MM3*, MMFF, AMBER*, and OPLSA*) implemented in MacroModel. Comparison of relative and absolute SFEs computed using either the GB/SA continuum model or MC/FEP calculations in the presence of explicit TIP4P water showed that, in general, relative SFEs can be estimated with greater accuracy. A second set of 20 mono- and difunctional molecules was also studied and relative SFEs estimated using energy minimization and thermodynamic cycle perturbation (TCP) protocols. SFEs calculated from TCP calculations using the GB/SA model were sensitive to bond lengths of dummy bonds (i.e., bonds involving dummy atoms). In such cases, keeping the bond lengths of dummy bonds close to the corresponding bond lengths of the starting structures improved the agreement of TCP-calculated SFEs with energy minimization results. Overall, these results indicate that GB/SA solvation free energy estimates from simple energy minimization calculations are of similar accuracy and value to those obtained using more elaborate TCP protocols. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 769–780, 1998     

Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH₄ at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (T_d5% up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan^® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme.