Chiral Supramolecular Nanotubes of Single‐Chain Magnets

We report a single‐chain magnet (SCM) made of a terbium(III) building block and a nitronyl‐nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long‐range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self‐organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each Tb^III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite‐size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (H_c=2400 Oe M_R=2.09 μ_B at 0.5 K) for this class of compounds.     

Total Synthesis of Tiacumicin B: Implementing Hydrogen Bond Directed Acceptor Delivery for Highly Selective β‐Glycosylations

A total synthesis of tiacumicin B, a natural macrolide whose remarkable antibiotic properties are used to treat severe intestinal infections, is reported. The strategy is in part based on the prior synthesis of the tiacumicin B aglycone, and on the decisive use of sulfoxides as anomeric leaving groups in hydrogen‐bond‐mediated aglycone delivery (HAD). This new HAD variant permitted highly β‐selective rhamnosylation and noviosylation. To increase convergence, the rhamnosylated C1–C3 fragment thus obtained was anchored to the C4–C19 aglycone fragment by adapting the Suzuki–Miyaura cross‐coupling used for the aglycone synthesis. Ring‐size‐selective macrolactonization provided a compound engaged directly in the noviolysation step with virtually total β selectivity. The final efficient removal of all the protecting groups provided synthetic tiacumicin B.     

Selective ortho-Functionalization of Adamantylarenes Enabled by Dispersion and an Air-Stable Palladium(I) Dimer

Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C−Br ortho to an adamantyl group is as favored as the corresponding adamantyl-free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of C−Br ortho to an adamantyl group, even if challenged with competing non-hindered C−OTf or C−Cl sites. The method makes use of an air-stable Pd^I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5–30 min.     

Solvent Impact on the Properties of Benchmark Metal–Organic Frameworks: Acetonitrile-Based Synthesis of CAU-10, Ce-UiO-66, and Al-MIL-53

Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal–organic frameworks (MOFs) CAU-10, Ce-UiO-66, and Al-MIL-53 of idealized composition [Al(OH)(ISO)], [Ce₆O₄(OH)₄(BDC)₆], and [Al(OH)(BDC)], respectively (ISO²⁻: isophthalate, BDC²⁻: terephthalate). Its use allowed the synthesis of Ce-UiO-66 on a gram scale. While CAU-10 and Ce-UiO-66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al-MIL-53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large-pore form over a broad temperature range (130–450 K). The stabilization of the large-pore form of Al-MIL-53 was attributed to a high percentage of noncoordinating −COOH groups as determined by solid-state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g⁻¹ within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).     

Preparation of Stereodefined Secondary Alkyllithium Compounds

We have developed a practical stereoretentive iodine/lithium‐exchange process that allows the stereodefined preparation of cis‐ and trans‐cycloalkyllithium compounds from their corresponding stereodefined iodides. Quenching with electrophiles offers stereospecific access to both cis‐ (up to 96 % cis) and trans‐cycloalkyl derivatives (up to 99 % trans). A detailed study of the thermodynamic stabilities, stereochemical behavior, and reactivities of axially and equatorially substituted cyclohexyllithium reagents is reported. Ab initio calculations demonstrate that the formation of oligomeric cyclohexyllithium structures is pivotal for explaining the observed stereochemical preference.     

Normal form and long time analysis of splitting schemes for the linear Schrödinger equation with small potential

We consider the linear Schrödinger equation on a one dimensional torus and its time-discretization by splitting methods. Assuming a non-resonance condition on the stepsize and a small size of the potential, we show that the numerical dynamics can be reduced over exponentially long time to a collection of two dimensional symplectic systems for asymptotically large modes. For the numerical solution, this implies the long time conservation of the energies associated with the double eigenvalues of the free Schrödinger operator. The method is close to standard techniques used in finite dimensional perturbation theory, but extended here to infinite dimensional operators.