Diastereoselective palladium-catalyzed alpha-arylation of 4-substituted cyclohexyl esters

A diastereoselective palladium-catalyzed arylation of 4-substituted cyclohexyl esters has been developed. The reaction proceeds at room temperature in the presence of [(t-Bu3P)PdBr]2 providing products in up to 37:1 dr.     

Ionization of aqueous toluic acids: Conductance and thermodynamics

Conductivities of aqueous solutions ofortho-, meta-, andpara-toluic acids have been measured for the concentration range 0.1–2 millimolar and at 5° intervals from 5 to 100°C. At each temperature pK _a(m) andA ₀ have been calculated using the paired ion model recently described by Fuoss. Thermodynamic parameters have been calculated for the ionization of each acid, and Walden products for the anions. Results are discussed in terms of contributions to acidity by enthalpy and entropy changes as well as by hydration of the various solute species.     

Preparation and decarboxylative rearrangement of (Z)-enyne esters

A method to assemble (Z)-enyne esters via palladium-catalyzed cross coupling reactions of enol tosylates is reported. A base-mediated one-pot decarboxylative rearrangement of the enynes to enones is described. The scope of this process is examined.     

Introducing oblique norms into multiple criteria programming

We propose to use block norms to generate nondominated solutions of multiple criteria programs and introduce the new concept of the oblique norm that is specially tailored to handle general problems. We prove the equivalence of finding the properly nondominated solutions of a multiple criteria program and solving its scalarization by means of oblique norms.     

Unilateral recurrent laryngeal nerve paralysis:The importance of “preoperative” voice therapy

This preliminary retrospective study of 19 female patients and 22male patients with unilateral recurrent nerve lesions demonstrated the promise of objective measurements in predicting the need for surgery, the efficacy of voice therapy in ameliorating vocal symptoms, and the effects of therapy in conjunction with surgery. Sixty-eight percent (68%) of the female patients and 64% of the male patients did not elect to have surgery. Outcome satisfaction of nonsurgical and surgical patients appeared to be similar. The data from this study support the importance of preoperative therapy for patients with unilateral vocal fold paralysis.     

George B. Dantzig and systems optimization

We pay homage to George B. Dantzig by describing a less well-known part of his legacy–his early and dedicated championship of the importance of systems optimization in solving complex real-world problems.     

Isotope‐Filtered 4D NMR Spectroscopy for Structure Determination of Humic Substances

Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global‐scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make‐up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to.