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.