Silylium-Ion-Promoted (3 + 2) Annulation of Allenylsilanes with Internal Alkynes Involving a Pentadienyl-to-Allyl Cation Electrocyclization.

A (3 + 2) annulation of allenyl- and, after rapid isomerization, propargylsilanes with internal 1-aryl-1-alkynes to form 4-methylenecyclopentenes is reported. The reaction is initiated by a silylium ion, and the catalytic cycle is subsequently maintained by the self-regeneration of the silylium-ion promoter. Unlike the well-established Danheiser annulation, where the allenylsilane serves as a , the present transformation engages the allenylsilane as a .

Sulfur hexafluoride multiple breath washin and washout outcomes in infants are not interchangeable.

Sulfur hexafluoride (SF) multiple-breath washout (MBW) assesses ventilation inhomogeneity, as an early marker of obstructive respiratory diseases. Primary outcomes are customarily washout-derived, and it is unclear whether the preceding SF-washin can provide similar estimates. We aimed to assess comparability of primary SF-MBW outcomes between washin and washout phases of infant SF-MBW data measured with the WBreath (ndd Medizintechnik AG, Zurich, Switzerland) and Spiroware (Eco Medics AG, Duernten, Switzerland) MBW-setups, respectively.

Kinetic Resolution of BINOLs and Biphenols by Atroposelective, Cu-H-Catalyzed Si-O Coupling with Hydrosilanes.

A nonenzymatic kinetic resolution of monoprotected BINOL and biphenol derivatives by atroposelective Si-O coupling with hydrosilanes is described. The reaction relies on a previously unprecedented Cu-H-catalyzed silylation of phenols. The catalyst system consisting of CuCl, (,)-Ph-BPE, and NaOBu enables the enantioselective coupling of the phenolic hydroxy group with a hydrosilane with moderate to good selectivity factors.

Enantio- and Diastereoselective Desymmetrization of 1,1'-Biaryl-2,6-Dicarbaldehydes by Copper-Catalyzed 1,2-Addition of Silicon Nucleophiles.

A desymmetrizing 1,2-addition of silicon nucleophiles to biaryl derivatives containing an 2,6-dicarbaldehyde-1-yl unit is reported. The reaction is catalyzed by copper with a triazolium-ion-derived N-heterocyclic carbene as the chiral ligand and makes use of an Si-B reagent as the silicon pronucleophile. The practical methodology furnishes axially chiral aromatic carbaldehydes decorated with a centrally chiral α-hydroxysilane moiety in moderate to good yields and with high enantio- as well as excellent diastereoselectivities.

Enantio- and Regioconvergent Nickel-Catalyzed Etherification of Phenols by Allylation to Access Chiral C(sp)-O Allyl Aryl Ethers.

An enantio- and regioconvergent allylation of phenols under nickel catalysis with an α-/γ-regioisomeric mixture of racemic silylated/germylated allylic chlorides is reported. The silyl/germyl group governs the regioselectivity, and the transformation affords enantiomerically enriched unsymmetrical 1,3-disubstituted allyl aryl ethers with excellent regiocontrol in good yields and excellent enantioselectivities. Notably, no nickel-mediated C-O bond activation is observed at room temperature.

Optimized algorithm for speed-of-sound-based infant sulfur hexafluoride multiple-breath washout measurements.

Introduction: Major methodological issues with the existing algorithm (WBreath) used for the analysis of speed-of-sound-based infant sulfur hexafluoride (SF) multiple-breath washout (MBW) measurements lead to implausible results and complicate the comparison between different age groups and centers.

Methods: We developed OASIS-a novel algorithm to analyze speed-of-sound-based infant SF MBW measurements. This algorithm uses known context of the measurements to replace the dependence of WBreath on model input parameters.

Ring Contraction of Saturated Cyclic Amines and Rearrangement of Acyclic Amines Through Their Corresponding Hydroxylamines.

Compared to modifications at the molecular periphery, skeletal adjustments present greater challenges. Within this context, skeletal rearrangement technology stands out for its significant advantages in rapidly achieving structural diversity. Yet, the development of this technology for ring contraction of saturated cyclic amines remains exceedingly rare.

Cationic Bis(hydrosilane)-Coinage-Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer-Sphere C=O Hydrosilylation Not Involving Metal Hydrides.

The preparation of cationic bis(hydrosilane)-coinage-metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BAr ] is described. Unlike previously reported hydrosilane-stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate (ortho-silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X-ray diffraction analysis, revealing that both Si-H bonds are activated by the Lewis acidic cationic metal center.

A computerized tool for the systematic visual quality assessment of infant multiple-breath washout measurements.

Background: Multiple-breath washout (MBW) is a sensitive method for assessing lung volumes and ventilation inhomogeneity in infants, but remains prone to artefacts (e.g., sighs).

Copper-catalyzed silylation of aryl and alkenyl triflates with silylboronic esters avoiding base-mediated borylation.

Silylation of aryl and alkenyl triflates is found to occur readily with silylboronic esters as a silicon source under copper catalysis. The silyl moieties are exclusively installed into the organic frameworks through the preferential generation of a silylcopper species, wherein base-mediated direct borylation is totally suppressed. The combined use of tri--butylphosphine and 4,4'-diphenyl-2,2'-bipyridine as a ligand combination turned out to be indispensable for achieving the high catalytic activity.

Enantioselective Dearomatization of Pyridinium Salts by Copper-Catalyzed C4-Selective Addition of Silicon Nucleophiles.

A copper-catalyzed C4-selective addition of silicon nucleophiles released from an Si-B reagent to prochiral pyridinium triflates is reported. The dearomatization proceeds with excellent enantioselectivity using Cu(CHCN)PF as the precatalyst and (R,R)-Ph-BPE (1,2-bis[(2R,5R)-2,5-diphenylphospholan-1-yl]ethane) as the chiral ligand. A carbonyl group at C3 is required for this, likely acting a weak donor group to preorganize and direct the nucleophilic attack towards C4.

Small molecule autoencoders: architecture engineering to optimize latent space utility and sustainability.

Autoencoders are frequently used to embed molecules for training of downstream deep learning models. However, evaluation of the chemical information quality in the latent spaces is lacking and the model architectures are often arbitrarily chosen. Unoptimized architectures may not only negatively affect latent space quality but also increase energy consumption during training, making the models unsustainable.

hCoCena: A toolbox for network-based co-expression analysis and horizontal integration of transcriptomic datasets.

As the number and complexity of transcriptomic datasets increase, there is a rising demand for accessible and user-friendly analysis tools. Here, we present hCoCena (horizontal construction of co-expression networks and analysis), a toolbox facilitating the analysis of a single dataset, as well as the joint analysis of multiple datasets. We describe steps for workspace setup, formatting tables, data processing, and network integration.

Electrophilic Activation of S-Si Reagents by Silylium Ions for Their Regio- and Diastereoselective Addition Across C-C Multiple Bonds.

A regioselective silylium-ion-promoted thiosilylation of internal C-C triple bonds with control over the double bond geometry is described. Both a C(sp)-S and a C(sp)-Si bond are formed with a trans relationship in this two-component reaction of an alkyne and a thiosilane. The resulting orthogonally functionalized C-C double bond can be chemoselectively defunctionalized or further processed by cross-coupling reactions with the alkene configuration retained.

Signal-correction errors in the EasyOne Pro LAB multiple-breath washout device significantly impact outcomes in children and adults.

Multiple-breath washout (MBW) is an established technique to assess functional residual capacity (FRC) and ventilation inhomogeneity in the lung. Indirect calculation of nitrogen concentration requires accurate measurement of gas concentrations. To investigate the accuracy of the CO concentration and molar mass (MM) values used for the indirect calculation of nitrogen concentration in a commercial MBW device [EasyOne Pro LAB (EOPL), ndd Medizintechnik AG, Switzerland] and its impact on outcomes.

Chiral Carborane Acids Decorated with Binol-Based Phosphonates: Synthesis, Characterization, and Application.

The syntheses of hexabrominated -carborates decorated with different chiral Binol-derived phosphonates and their conjugate acids are described. X-ray diffraction analysis reveals a polymeric structure for the sodium salt with the anionic units connected by [B-Br-Na-O═P] linkages. For the acid, coordination of the proton to the phosphonate's P═O oxygen atom is assumed.

Ligand-Controlled On-Off Switch of a Silicon-Tethered Directing Group Enabling the Regiodivergent Hydroalkylation of Vinylsilanes under Ni-H Catalysis.

A regiodivergent Ni-H-catalyzed hydroalkylation of vinylsilanes is described. Depending on the ancillary ligand at the nickel catalyst, the regioselectivity can be steered by a directing group attached to the silicon atom. The mild protocols allow for the selective synthesis of either branched or linear alkylsilanes.

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes.

Aryl- and alkyldiimides (R-N═NH with R = aryl or alkyl) are elusive intermediates of valuable synthetic use, as they are assumed to be transient species in processes involving both carbon (with concomitant loss of N) and nitrogen nucleophiles (with conservation of the N═N moiety). The actual compounds are fragile and as such not bench stable which is why they have not yet found the attention they deserve. Conversely, early contributions showed that the stability of the parent diimide is significantly increased by replacing the hydrogen atom by a silyl group, but the synthetic applicability of these silicon-protected aryl- and alkyldiazenes has been far less explored, in part due to the absence of general procedures for their preparation.

Arenium-ion-catalysed halodealkylation of fully alkylated silanes.

'Organic silicon' is not found in nature but modern chemistry is hard to imagine without silicon bound to carbon. Although silicon-containing commodity chemicals such as those emerging from the 'direct process' look simple, it is not trivial to selectively prepare aryl-substituted and alkyl-substituted (functionalized) silicon compounds, known as silanes. Chlorosilanes such as MeSiCl (n = 1-3) as well as SiCl (n = 4) are common starting points for the synthesis of silicon-containing molecules.

Fluoride-Catalyzed Arylation of α-(Trifluoromethyl)styrene Derivatives with Silicon-Masked, Functionalized Aryl Pronucleophiles.

An operationally simple transition-metal-free protocol for the arylation of α-(trifluoromethyl)styrene derivatives with silicon-protected functionalized aryl pronucleophiles is disclosed. Catalytic amounts of an anionic Lewis base such as fluoride trigger the release of the aryl nucleophile from -aryl--silyldiazenes by desilylation along with denitrogenation. The thus-generated carbon nucleophiles engage in an allylic displacement with α-(trifluoromethyl)styrene electrophiles to afford the corresponding geminal difluoroalkenes.

Dehydrative Coupling of 1,1-Diarylalkenes and Cyclohexa-2,5-diene-1-carbaldehyde Derivatives Induced by a B(CF)-Initiated [1,2]-Alkyl Migration.

A four-step formal allylation of benzoic acid derivatives involving a B(CF)-initiated and proton-catalyzed [1,2]-alkyl shift as part of a dehydrative coupling of cyclohexa-2,5-diene-1-carbaldehyde derivatives and 1,1-diarylalkenes is reported. By this, a series of allyl arenes can be regioselectively obtained from readily available benzoic acids in good yields.

Regioselective Hydroalkylation of Vinyl- and Allylsilanes as Well as Vinylgermanes under Ni-H Catalysis.

A Ni-H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides is reported. Unlike related reactions of styrene or vinyl boronate esters, the addition across the C-C double bond proceeds with anti-Markovnikov selectivity to deliver the linear regioisomer. Mechanistic control experiments support a radical mechanism, and a competition experiment reveals that the chemoselectivity is in favor of the vinyl over the allyl group.

Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis.

Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and / selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high / selectivity (up to >96 : 4) is reported.