BH3-catalyzed oligomerization of ethyl diazoacetate: the role of C-boron enolates

In contrast to trialkyl boranes, the reaction of borane (BH3) and ethyl diazoacetate (EDA) generates dimer, trimer, and oligomers of EDA. The products arise from double, triple, and multiple insertions of CHCO2Et groups in B-C bonds. On the basis of NMR spectroscopic data, trapping experiments, and computational studies, a novel C-boron enolate has been identified as a key intermediate in this reaction. This C-boron enolate species is calculated to be 7.1 kcal/mol (gas phase) more stable than its isomeric O-boron enolate form. Both spectroscopic data and trapping results also reveal the formation of a doubly borylated enolate generated as a side product by a proton transfer between the C- and O-boron monoenolates.     

An approach to the synthesis of stenine

A type 2 N-acylnitroso intramolecular Diels-Alder reaction followed by reductive N-O bond cleavage formed the B and C rings of the Stemona alkaloid stenine. Further elaboration provided the functionalized tricyclic core.     

Organo-silica hybrid functional nanomaterials: how do organic bridging groups and silsesquioxane moieties work hand-in-hand?

Bridged polysilsesquioxanes (BPS) are a class of versatile functional hybrid materials with tunable chemical, physical and mechanical properties. This tutorial review describes recent advances of these functional hybrid nanomaterials. The review includes control of factors affecting nanometre scale morphology, the preparation of spherical hybrid nanoparticles, along with applications in fields including energy, optics and electronics. Special emphasis will be made regarding the synergy between the organic component of the hybrid material and the polysilsesquioxane moieties.     

Adsorption of PTCDI on Au(1 1 1): Photoemission and scanning tunnelling microscopy

The adsorption of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI) on Au(1 1 1) has been studied using synchrotron-based X-ray photoelectron spectroscopy and in situ scanning tunnelling microscopy. Direct topographic and surface coverage information provided by the scanning probe measurements have enabled us to correlate peaks in the relatively complex carbon core-level photoemission to interactions of the surface with different parts of the PTCDI molecule. A strong interaction between the imide ends of the molecule with the underlying gold substrate is evidenced by a large chemical shift in the imide carbon peaks, which is observed only for the first adsorbed layer.     

Regioselective SNAr reactions of substituted difluorobenzene derivatives: practical synthesis of fluoroaryl ethers and substituted resorcinols

In this Letter, we describe a practical and highly selective method for the preparation of fluoroaryl ethers and differentially substituted resorcinol derivatives. This synthetic strategy relies on a selective S_NAr of substituted difluorobenzene derivatives with various alcohols.     

Overhauser dynamic nuclear polarization and molecular dynamics simulations using pyrroline and piperidine ring nitroxide radicals

The efficiency of Overhauser dynamic nuclear polarization (DNP) depends on the local dynamics modulating the dipolar coupling between the two interacting spins. By attaching nitroxide based spin labels to molecules and by measuring the ¹H DNP response of solvent water, information about the local hydration dynamics near the spin label can be obtained. However, there are two commonly used types of nitroxide ring structures; a pyrroline based and a piperidine based molecule. It is important to know when comparing different experiments, whether changes in DNP enhancements are due to changes in local hydration dynamics or because of the different spin label structures. In this study we investigate the key parameters affecting DNP signal enhancements for 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl, a 5-membered ring nitroxide radical, and for 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, a 6-membered ring nitroxide radical. Using X-Band DNP, field cycling relaxometry, and molecular dynamics simulations, we conclude that the key parameters affecting the DNP amplitude of the ¹H signal of water to be equal when using either nitroxide. Thus, experiments measuring hydration dynamics using either type of spin labels may be compared.     

Identification of major proton fluence events from nitrates in polar ice cores.

Large transient concentrations of nitrates in polar ice cores have been identified as the signature of some major solar proton fluence events between 1940 and 1991. We review this solar proton proxy identification technique using nitrate concentration measurements in ice cores from the Arctic and Antarctic. Using this identification technique we go back in time in an attempt to identify major solar proton events during the past several centuries. There is a very large nitrate increase corresponding to the Carrington flare of 1859 evident in the Arctic ice core. Other significant nitrate increases may indicate that major solar proton events occurred toward the end of the last century. The problems associated with this new technique of using nitrates as proxies to identify solar proton events are discussed.