9-Borabicyclo[3.3.2]decanes and the asymmetric hydroboration of 1,1-disubstituted alkenes

The syntheses of the optically pure asymmetric hydroborating agents 1 (a, R = Ph; b, R = TMS) in both enantiomeric forms are reported. These reagents are effective for the hydroboration of cis-, trans- and trisubstituted alkenes. More significantly, they exhibit unprecedented levels of selectivity in the asymmetric hydroboration of 1,1-disubstituted alkenes (28-92% ee), a previously unanswered challenge in the nearly 50 year history of this reagent-controlled process. For example, the hydroboration of alpha-methylstyrene with 1a produces the corresponding alcohol 6f in 78% ee (cf., Ipc2BH, 5% ee). Suzuki coupling of the intermediate adducts 5 produces the nonracemic products 7 very effectively (50-84%) without loss of optical purity.     

Branching Rules for Finite-Dimensional $\mathcal {U}_{q}(\mathfrak {su}(3))$-Representations with Respect to a Right Coideal Subalgebra

We consider the quantum symmetric pair \((\mathcal {U}_{q}(\mathfrak {su}(3)), \mathcal {B})\) where \(\mathcal {B}\) is a right coideal subalgebra. We prove that all finite-dimensional irreducible representations of \(\mathcal {B}\) are weight representations and are characterised by their highest weight and dimension. We show that the restriction of a finite-dimensional irreducible representation of \(\mathcal {U}_{q}(\mathfrak {su}(3))\) to \(\mathcal {B}\) decomposes multiplicity free into irreducible representations of \(\mathcal {B}\). Furthermore we give explicit expressions for the highest weight vectors in this decomposition in terms of dual q-Krawtchouk polynomials.     

Matrix-valued orthogonal polynomials related to the quantum analogue of $$(\mathrm{SU}(2) \times \mathrm{SU}(2), \mathrm{diag})$$

Matrix-valued spherical functions related to the quantum symmetric pair for the quantum analogue of \((\mathrm{SU}(2) \times \mathrm{SU}(2), \mathrm{diag})\) are introduced and studied in detail. The quantum symmetric pair is given in terms of a quantised universal enveloping algebra with a coideal subalgebra. The matrix-valued spherical functions give rise to matrix-valued orthogonal polynomials, which are matrix-valued analogues of a subfamily of Askey–Wilson polynomials. For these matrix-valued orthogonal polynomials, a number of properties are derived using this quantum group interpretation: the orthogonality relations from the Schur orthogonality relations, the three-term recurrence relation and the structure of the weight matrix in terms of Chebyshev polynomials from tensor product decompositions, and the matrix-valued Askey–Wilson type q-difference operators from the action of the Casimir elements. A more analytic study of the weight gives an explicit LDU-decomposition in terms of continuous q-ultraspherical polynomials. The LDU-decomposition gives the possibility to find explicit expressions of the matrix entries of the matrix-valued orthogonal polynomials in terms of continuous q-ultraspherical polynomials and q-Racah polynomials.     

Spontaneous CO Release from RuII(CO)2–Protein Complexes in Aqueous Solution,Cells, and Mice

We demonstrate that Ru^II(CO)₂–protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac‐RuCl(κ²‐H₂NCH₂CO₂)(CO)₃] (CORM‐3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO‐responsive turn‐on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM‐3. CO released from a synthetic bovine serum albumin (BSA)–Ru^II(CO)₂ complex leads to downregulation of the cytokines interleukin (IL)‐6, IL‐10, and tumor necrosis factor (TNF)‐α in cancer cells. Finally, administration of BSA–Ru^II(CO)₂ in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of Ru^II(CO)₂–protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo.     

Metalloenzyme‐Like Zeolites as Lewis Acid Catalysts for CC Bond Formation

The use of metalloenzyme‐like zeolites as Lewis acid catalysts for C? C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass‐derived compounds. The discovery of new Diels–Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl–ene reactions have given a further boost to this rapidly evolving field.     

Energy scaling-up of stable single filament

The influence of the input pulse chirp and energy on the filamentation process is studied. Output beam profiles, spectra and energies were systematically measured by changing the pulse chirp for different input energies. A map of the different energy-chirp regions was compiled. It shows that high-energy stable single filament can be obtained by using chirped input pulses, allowing the scaling-up of the energy throughput in the filament. Moreover, under high-energy regimes nonlinear effects induced by chirped pulses could produce pulse post-compression.