C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KOtBu: Unusual Regioselectivity through a Radical Mechanism

We report a C?C bond‐forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KO^tBu to form α‐alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways.     

A Molecular Secret Sharing Scheme

A method for implementing a secret sharing scheme at the molecular level is presented. By creating molecular code generators that are self‐assembled from several molecular components, we established a means for distributing distinct code‐activating elements among several participants. In this way, an authorization code can only be generated when all the participants are present, which ensures that highly secured systems cannot be operated by unauthorized individuals or disloyal users. Additional layers of protection result from the ability to program the security code by replacing one or several molecular components and by subjecting the system to distinct chemical inputs.     

A Macrocyclic Furan with Accessible Oxidation States: Switching Between Aromatic and Antiaromatic Global Ring Currents

Macrocyclic furans are predicted to switch between global aromaticity and antiaromaticity, depending on their oxidation states. However, the macrocyclic furans reported to date are stabilized by electron withdrawing groups, which result in inaccessible oxidation states. To circumvent this problem, a post-macrocyclization approach was applied to introduce methylene-substituted macrocyclic furans, which display an extremely low oxidation potential of −0.23 vs. Fc/Fc⁺, and are partially oxidized in ambient conditions. Additional oxidation to the dication results in aromaticity switching to a global 30πe⁻ aromatic state, as indicated by the formation of a strong diatropic current observed in the ¹H NMR spectrum. NICS and ACID calculations support this trend and provide evidence for a different pathway for the global current in the neutral and dicationic states. According to these findings, macrocyclic furans can be rendered as promising p-type materials with stable oxidation states.     

Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom

The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [Co^IIIW₁₂O₄₀]^5? as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H₂O→ArOH+H₂. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO₂ and H₂ is a side‐reaction.     

Controlling switching in bistable [2]catenanes by combining donor-acceptor and radical-radical interactions

Two redox-active bistable [2]catenanes composed of macrocyclic polyethers of different sizes incorporating both electron-rich 1,5-dioxynaphthalene (DNP) and electron-deficient 4,4'-bipyridinium (BIPY(2+)) units, interlocked mechanically with the tetracationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT(4+)), were obtained by donor-acceptor template-directed syntheses in a threading-followed-by-cyclization protocol employing Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloadditions in the final mechanical-bond forming steps. These bistable [2]catenanes exemplify a design strategy for achieving redox-active switching between two translational isomers, which are driven (i) by donor-acceptor interactions between the CBPQT(4+) ring and DNP, or (ii) radical-radical interactions between CBPQT(2(?+)) and BIPY(?+), respectively. The switching processes, as well as the nature of the donor-acceptor interactions in the ground states and the radical-radical interactions in the reduced states, were investigated by single-crystal X-ray crystallography, dynamic (1)H NMR spectroscopy, cyclic voltammetry, UV/vis spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy. The crystal structure of one of the [2]catenanes in its trisradical tricationic redox state provides direct evidence for the radical-radical interactions which drive the switching processes for these types of mechanically interlocked molecules (MIMs). Variable-temperature (1)H NMR spectroscopy reveals a degenerate rotational motion of the BIPY(2+) units in the CBPQT(4+) ring for both of the two [2]catenanes, that is governed by a free energy barrier of 14.4 kcal mol(-1) for the larger catenane and 17.0 kcal mol(-1) for the smaller one. Cyclic voltammetry provides evidence for the reversibility of the switching processes which occurs following a three-electron reduction of the three BIPY(2+) units to their radical cationic forms. UV/vis spectroscopy confirms that the processes driving the switching are (i) of the donor-acceptor type, by the observation of a 530 nm charge-transfer band in the ground state, and (ii) of the radical-radical ilk in the switched state as indicated by an intense visible absorption (ca. 530 nm) and near-infrared (ca. 1100 nm) bands. EPR spectroscopic data reveal that, in the switched state, the interacting BIPY(?+) radical cations are in a fast exchange regime. In general, the findings lay the foundations for future investigations where this radical-radical recognition motif is harnessed in bistable redox-active MIMs in order to achieve close to homogeneous populations of co-conformations in both the ground and switched states.     

Using a nanoelectrospray-differential mobility spectrometer-mass spectrometer system for the analysis of oligosaccharides with solvent selected control over ESI aggregate ion formation

Differential mobility spectrometry (DMS), also commonly referred to as high field asymmetric waveform ion mobility spectrometry (FAIMS) is a rapidly advancing technology for gas-phase ion separation. The interfacing of DMS with mass spectrometry (MS) offers potential advantages over the use of mass spectrometry alone. Such advantages include improvements to mass spectral signal/noise, orthogonal/complementary ion separation to mass spectrometry, enhanced ion and complexation structural analysis, and the potential for rapid analyte quantitation. In this report, we demonstrate the successful use of our nanoESI-DMS-MS system, with a methanol drift gas modifier, for the separation of oligosaccharides. The tendency for ESI to form oligosaccharide aggregate ions and the negative impact this has on nanoESI-DMS-MS oligosaccharide analysis is described. In addition, we demonstrate the importance of sample solvent selection for controlling nanoESI oligosaccharide aggregate ion formation and its effect on glycan ionization and DMS separation. The successful use of a tetrachloroethane/methanol solvent solution to reduce ESI oligosaccharide aggregate ion formation while efficiently forming a dominant MH(+) molecular ion is presented. By reducing aggregate ion formation in favor of a dominant MH(+) ion, DMS selectivity and specificity is improved. In addition to DMS, we would expect the reduction in aggregate ion complexity to be beneficial to the analysis of oligosaccharides for other post-ESI separation techniques such as mass spectrometry and ion mobility. The solvent selected control over MH(+) molecular ion formation, offered by the use of the tetrachloroethane/methanol solvent, also holds promise for enhancing MS/MS structural characterization analysis of glycans.     

Hard Sard: Quantitative Implicit Function and Extension Theorems for Lipschitz Maps

We prove a global implicit function theorem. In particular we show that any Lipschitz map ${f : \mathbb{R}^{n} \times \mathbb{R}^{m} \rightarrow \mathbb{R}^{n}}$ (with n-dim. image) can be precomposed with a bi-Lipschitz map ${\bar{g} : \mathbb{R}^{n} \times \mathbb{R}^{m} \rightarrow \mathbb{R}^{n} \times \mathbb{R}^{m}}$ such that ${f \circ \bar{g}}$ will satisfy, when we restrict to a large portion of the domain ${E \subset \mathbb{R}^{n} \times \mathbb{R}^{m}}$ , that ${f \circ \bar{g}}$ is bi-Lipschitz in the first coordinate, and constant in the second coordinate. Geometrically speaking, the map ${\bar{g}}$ distorts ${\mathbb{R}^{n+m}}$ in a controlled manner so that the fibers of f are straightened out. Furthermore, our results stay valid when the target space is replaced by any metric space. A main point is that our results are quantitative: the size of the set E on which behavior is good is a significant part of the discussion. Our estimates are motivated by examples such as Kaufman’s 1979 construction of a C ¹ map from [0, 1]³ onto [0, 1]² with rank ≤ 1 everywhere. On route we prove an extension theorem which is of independent interest. We show that for any D ≥ n, any Lipschitz function ${f : [0,1]^{n} \rightarrow \mathbb{R}^{D}}$ gives rise to a large (in an appropriate sense) subset ${E \subset [0,1]^{n}}$ such that ${f|_E}$ is bi-Lipschitz and may be extended to a bi-Lipschitz function defined on all of ${\mathbb{R}^{n}}$ . This extends results of Jones and David, from 1988. As a simple corollary, we show that n-dimensional Ahlfors–David regular spaces lying in ${\mathbb{R}^{D}}$ having big pieces of bi-Lipschitz images also have big pieces of big pieces of Lipschitz graphs in ${\mathbb{R}^{D}}$ . This was previously known only for D ≥ 2n?+?1 by a result of David and Semmes.     

Subsets of rectifiable curves in Hilbert space-the analyst’s TSP

We study one dimensional sets (Hausdorff dimension) lying in a Hilbert space. The aim is to classify subsets of Hilbert spaces that are contained in a connected set of finite Hausdorff length. We do so by extending and improving results of Peter Jones and Kate Okikiolu for sets in ℝ^d. Their results formed the basis of quantitative rectifiability in ℝ^d. We prove a quantitative version of the following statement: a connected set of finite Hausdorff length (or a subset of one), is characterized by the fact that inside balls at most scales aroundmost points of the set, the set lies close to a straight line segment (which depends on the ball). This is done via a quantity, similar to the one introduced in [Jon90], which is a geometric analogue of the Square function. This allows us to conclude that for a given set K, the ℓ₂ norm of this quantity (which is a function of K) has size comparable to a shortest (Hausdorff length) connected set containing K. In particular, our results imply that, with a correct reformulation of the theorems, the estimates in [Jon90, Oki92] are independent of the ambient dimension.