Assessing diffusive fluxes and pore water radon activities via a single automated experiment

We present a laboratory system to evaluate radon flux and pore water radon via automated sediment equilibration experiments. The setup includes a measured mass of sediment and water inside a gas-tight reaction flask connected in a closed loop to a radon-in-air analyzer. Diffusive fluxes are determined either from the near-linear slope of the activity versus time over the first several hours or by running the experiment longer to estimate the equilibrium concentration via a curve fitting approach. By combining the equilibrium activity with relevant physical parameters, one can also estimate the pore water concentrations.     

Radical Cyclization/ipso‐1,4‐Aryl Migration Cascade: Asymmetric Synthesis of 3,3‐Difluoro‐2‐propanoylbicyclo[3.3.0]octanes

A novel method for the asymmetric synthesis of 3,3‐difluoro‐2‐propanoylbicyclo‐[3.3.0]octanes involves an unprecedented intramolecular radical cyclization/ipso‐1,4‐aryl migration cascade.     

Synthesis and spectroscopic characterization of red-shifted spironaphthoxazine based optical switch probes

Spironaphthoxazine (NISO) is an efficient optical switch probe that has applications in high contrast detection of Förster resonance energy transfer (FRET) using optical lock-in detection (OLID). NISO exists in two distinct states, spiro (SP) and merocyanine (MC), that can be independently controlled by using alternate irradiation with near ultraviolet and visible light. Unfortunately, the SP-state of NISO has an absorption centered at 350 nm, which may lead to phototoxic effects when manipulating the probe within a living cell. To overcome this problem we introduce new, red-shifted amino-substituted NISO probes compared to NISO that undergo an efficient SP to MC transition in response to irradiation by using 405-nm light, which is less damaging to living cells. This study details the synthesis of amino-substituted NISO and their N-hydroxysuccinimide ester and maleimide derivatives and their use in generating covalent attached protein conjugates. This study also presents a characterization of the spectroscopic and optical switching properties of these red-shifted NISO probe in solution.     

Synthesis of gem-difluoromethylenated bicyclo[m.n.0]alkan-1-ols and their ring-expansion to gem-difluoromethylenated macrocyclic lactones

Fluoride-catalyzed stereoselective nucleophilic addition of PhSCF(2)SiMe(3) (1) to α-carboethoxycycloalkanones 2 followed by intramolecular radical cyclization of the resulting cis-3 adduct afforded the corresponding gem-difluoromethylenated bicyclic compounds 4, which underwent ring-expansion followed by the Baeyer-Villiger-type oxidation of the resulting macrocyclic ketone intermediates to give gem-difluoromethylenated macrocyclic lactones 5.     

The Morita?Baylis?Hillman Reaction of Chiral Highly Oxygenated Cyclopent‐2‐enones

The Morita? Baylis? Hillman (MBH) reactions of (4S,5R,7R,8R)‐ and (4R,5R,7R,8R)‐4‐hydroxy‐7,8‐dimethoxy‐7,8‐dimethyl‐6,9‐dioxaspiro[4.5]dec‐2‐en‐1‐ones ( 2 and 3 , resp.) with aldehydes using various catalysts were studied. A combination of Bu₃P/phenol in THF was found being optimum conditions giving the corresponding MBH adducts with high diastereoisomeric ratios. After separation, each stereomerically pure isomer of the MBH adducts was subjected to hydrolysis employing 1% aq. CF₃COOH (TFA) in a water bath of an ultrasonic cleaner to afford the corresponding polyhydroxylated cyclopentenones in good yields.     

Lanthanide triflate catalyzed generation of N-acyliminium ions from α-amido sulfones: the synthesis of (1-alkyl-1-aryl)methyl phenyl sulfones

The reaction of α-amido sulfones with various aromatic and heteroaromatic compounds in the presence of a catalytic amount of lanthanide triflate provides a facile route for the synthesis of (1-alkyl-1-aryl)methyl phenyl sulfones.     

Flow-injection in-line complexation for ion-pair reversed phase high performance liquid chromatography of some metal-4-(2-pyridylazo) resorcinol chelates

Flow injection (FI) was coupled to ion-pair reversed phase high performance liquid chromatography (IP-RPHPLC) for the simultaneous analysis of some metal-4-(2-pyridylazo) resorcinol (PAR) chelates. A simple reverse flow injection (rFI) set-up was used for in-line complexation of metal-PAR chelates prior to their separation by IP-RPHPLC. The rFI conditions were: injection volume of PAR 85 μL, flow rate of metal stream 4.5 mL min⁻¹, concentration of PAR 1.8 × 10⁻⁴ mol L⁻¹ and the mixing coil length of 150 cm. IP-RPHPLC was carried out using a C₁₈ μBondapak column with the mobile phase containing 37% acetonitrile, 3.0 mmol L⁻¹ acetate buffer pH 6.0 and 6.2 mmol L⁻¹ tetrabutylammonium bromide (TBABr) at a flow rate of 1.0 mL min⁻¹ and visible detection at 530 and 440 nm. The analysis cycle including in-line complexation and separation by IP-RPHPLC was 16 min, which able to separate Cr(VI) and the PAR chelates of Co(II), Ni(II) and Cu(II).     

Efficient synthesis of alkyl 2,3-unsaturated glucopyranosides from glycals mediated by ytterbium(III) triflate-trialkyl aluminum

Treatment of glycals with trialkylaluminum in the presence of a catalytic amount of Yb(OTf)₃ leads to the corresponding alkyl 2,3-unsaturated glycosides in good to excellent yields. Reactions of protected glycals are achieved under very mild conditions.     

Mild Oxidation of Alcohols with o‐Iodoxybenzoic Acid (IBX) in a Water/CH2Cl2 Mixture in the Presence of Phase‐Transfer Catalyst

A mild oxidation of alcohols to the respective carbonyl compounds with o‐iodoxybenzoic acid (IBX) catalyzed by n‐Bu₄NBr in a water/dichloromethane (1:1) mixture is described. The method offers the advantage of a simple, inexpensive catalyst and the diminution of organic solvent employed in the reaction.