Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles

β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.     

Phosphinine-Based Ligands in Gold-Catalyzed Reactions

A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%V_bur) was calculated to get insight into the steric properties, [LNi(CO)₃] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. Au^I coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of P^III compounds were successfully used in the Au^I-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts.     

Inverse electron demand hetero-Diels–Alder reaction in preparing 1,4-benzodioxin from o-quinone and enamine

A process for synthesizing 1,4-benzodioxin, through oxidation of a phenol to an o-quinone followed by treatment with an enamine, has been developed. Adduct stereochemistry is found to be retained via this one-pot reaction. The method uses hypervalent iodine reagent under mild conditions and is compatible with a wide scope of phenols and enamines.     

EELS measurements of boron concentration profiles in p-a-Si and nip a-Si solar cells

The p-type Si layer in a-Si and μc-Si solar cells on foil needs to fulfil several important requirements. The layer is necessary to create the electric field that separates the photo-generated charge carriers; the doping also increases the conductivity to conduct the photocurrent to the front contact; on the other hand, the p-layer should transmit the incident light efficiently to the intrinsic absorber layer. We show that it is possible to study TEM samples prepared, for analysis of possible layer defects, by focussed ion beam milling to detect boron and carbon concentrations as low as 10²⁰ cm^-3, using core-loss EELS combined with numerical analysis. We control the band gap and activation energy of p-a-SiC by varying the B₂H₆ and CH₄ flow during deposition in the process chamber. We have found a linear relation between the activation energy of the dark conductivity E_act and the optical band gap E₀₄. Modelling shows that the optimum efficiency in nip solar cells is obtained when the p-a-SiC band gap is slightly larger than the band gap of the absorber layer. We have assessed the potential of core-loss EELS for detecting B and C concentrations as low as 10²⁰ cm^-3 in a spatially resolved manner, and of low-loss EELS as a probe of the local variations in plasmon energy.     

Group Theory,Computational Thinking,and Young Mathematicians

In this article, we investigate the artistic puzzle of designing mathematics experiences (MEs) to engage young children with ideas of group theory, using a combination of hands-on and computational thinking (CT) tools. We elaborate on: (1) group theory and why we chose it as a context for young mathematicians’ experiences with symmetry and transformations; (2) our ME design principles of agency, access, surprise and audience; (3) the affordances of CT that complement our design principles; and (4) three ME variations we tested in grades 3–6 classrooms. We then reflect on the ME variations based on our design principles and the affordances of CT, and consider how the MEs may be further adapted and improved.