Pd-catalyzed aryl amination mediated by well defined, N-heterocyclic carbene (NHC)-Pd precatalysts, PEPPSI

Pd-N-heterocyclic carbene (NHC)-catalyzed Buchwald-Hartwig amination protocols mediated by Pd-PEPPSI precatalysts is described. These protocols provide access to a range of hindered and functionalized drug-like aryl amines in high yield with both electron-deficient and electron-rich aryl- and heteroaryl chlorides and bromides. Variations in solvent polarity, base and temperature are tolerated, enhancing the scope and utility of this protocol. A mechanistic rationalization for base strength (pKb) requirements is also provided.     

Polymer‐coated Boron Doped Diamond Optically Transparent Electrodes for Spectroelectrochemical Sensors

Spectroelectrochemical sensors combine electrochemistry, spectroscopy, and partitioning into a film to provide improved selectivity for the target analyte. The sensor usually consists of an optically transparent electrode (OTE) coated with a charge selective polymer film. The polymer film is chosen to pre‐concentrate analyte at the OTE surface to improve the sensitivity and provide selectivity against like charged interferences. OTEs such as Indium Tin Oxide (ITO) have been used extensively for spectroelectrochemical sensors, but little is known about the applicability of such sensors using other OTE materials, such as Boron Doped Diamond (BDD). One distinct advantage of BDD OTEs over ITO OTEs is their significant increase in sensitivity for organic compounds, such as 4‐aminophenol and hydroquinone. We have developed absorption and fluorescence‐based sensing methods with a BDD OTE coated with a sulfonated ionomer film, Nafion. This is demonstrated with tris(2,2′‐bipyridyl)ruthenium(II) ion [Ru(bpy)₃²⁺] using an attenuated total reflectance (ATR) flow cell setup for both absorption and fluorescence. With a Nafion coated BDD optically transparent thin layer electrode (OTTLE), we developed a fluorescence based sensor for a common polyaromatic hydrocarbon (PAH), 1‐hydroxypyrene (1‐pyOH), achieving a detection limit of 80 nM (17 ppb). This work manifests new sensing applications while broadening the use of spectroelectrochemistry, OTEs, and BDD as an electrode material.     

Phase-tunable fluorophores based upon benzobis(imidazolium) salts

A new series of highly photoluminescent benzobis(imidazolium) salts with tunable electronic and physical properties is described. Systematic structural manipulations provided a set of materials that were not only fluorescent in the condensed state but also displayed tunable glass transition temperatures ranging from -0.3 to 113 degrees C. Upon heating, these robust materials flowed while maintaining their emissive properties. Further phase tuning was demonstrated through the synthesis of two thermotropic liquid-crystalline fluorescent benzobis(imidazolium) salts.     

Single-Shot Diffusion Measurement in Laser-Polarized Gas

A single-shot pulsed gradient stimulated echo sequence is introduced to address the challenges of diffusion measurements of laser polarized 3He and 129Xe gas. Laser polarization enhances the NMR sensitivity of these noble gases by >10(3), but creates an unstable, nonthermal polarization that is not readily renewable. A new method is presented which permits parallel acquisition of the several measurements required to determine a diffusive attenuation curve. The NMR characterization of a sample's diffusion behavior can be accomplished in a single measurement, using only a single polarization step. As a demonstration, the diffusion coefficient of a sample of laser-polarized 129Xe gas is measured via this method.     

Control by Ring Substitution of the Conformation Change Dynamics in Photochromic Polypeptides

Abstract— In order to develop new systems that couple photochromism with molecular conformation change, a series of spiropyrans having different ring substituents were attached to poly(L-glutamic acid). The polypeptides were dissolved in hexafluoroisopropanol and dark adapted so that the dye was in the merocyanine form. Following adaptation by white light and dye photoconversion from the merocyanine to spiropyran forms, polypeptide dark-adaptation kinetics were monitored by circular dichroism (CD) and dye dark adaptation was monitored by UV/ visible. Light adaptation caused a light-induced coil-to-helix transition, with dark adaptation resulting in relaxation back to the coil. The dark-adaptation rate constant measured by UV/visible was equal to that measured by CD, demonstrating close coupling between dye state and polypeptide conformation. By varying the substituents on the spiropyran ring, dark-adaptation half lives were varied from less than a minute to 2 h, representing nearly three orders of magnitude.     

A new type of edge-derived vertex coloring

We study the minimum number of weights assigned to the edges of a graph G with no component K₂ so that any two adjacent vertices have distinct sets of weights on their incident edges. The best possible upper bound on this parameter is proved.     

Neutral high-potential nickel triad bisdithiolenes: structure and solid-state NMR properties of Pt[S2C2(CF3)2]2

X-ray crystallography and solid-state NMR techniques were used to determine the structure and 195Pt NMR chemical shift (CS) tensor of Pt[S2C2(CF3)2]2. This is the first reported crystal structure of a highly oxidizing (CN- or CF3-substituted) neutral bis(dithiolene) complex of a Ni triad metal in its pure form. The 195Pt NMR CS tensor is highly anisotropic and asymmetric; the latter property is attributed to the noninnocent nature of the ligand. The tensor components and orientation are determined with density functional theory calculations.     

A user-friendly, all-purpose Pd-NHC (NHC=N-heterocyclic carbene) precatalyst for the negishi reaction: a step towards a universal cross-coupling catalyst

We have developed the first user-friendly Negishi protocol capable of routinely cross-coupling all combinations of alkyl and aryl centers. The use of an easily synthesized, air stable, highly active, well-defined precatalyst PEPPSI-IPr (1; PEPPSI=pyridine-enhanced precatalyst preparation, stabilization and initiation; IPr=diisopropylphenylimidazolium derivative) substantially increases the scope, reliability, and ease-of-use of the Negishi reaction. All organohalides and routinely used pseudohalides were excellent coupling partners, with the use of chlorides, bromides, iodides, triflates, tosylates, and mesylates resulting in high yield of the coupled product. Furthermore, all reactions were performed by using general laboratory techniques, with no glove-box necessary as the precatalyst was weighed and stored in air. Utilization of this methodology allowed for the easy synthesis of an assortment of sterically encumbered biaryls and druglike heteroaromatics, demonstrating the value of the PEPPSI-IPr system. Furthermore, this is also the first time Pd-NHC (NHC=N-heterocyclic carbene) methodology has surpassed the related phosphine-ligated Negishi processes both in activity and use.     

Easily prepared air- and moisture-stable Pd-NHC (NHC=N-heterocyclic carbene) complexes: a reliable, user-friendly, highly active palladium precatalyst for the Suzuki-Miyaura reaction

The synthesis of NHC-PdCl(2)-3-chloropyridine (NHC=N-heterocyclic carbene) complexes from readily available starting materials in air is described. The 2,6-diisopropylphenyl derivative was found to be highly catalytically active in alkyl-alkyl Suzuki and Negishi cross-coupling reactions. The synthesis, ease-of-use, and activity of this complex are substantial improvements over in situ catalyst generation and all current Pd-NHC complexes. The utilization of complex 4 led to the development of a reliable, easily employed Suzuki-Miyama protocol. Employing various reaction conditions allowed a large array of hindered biaryl and drug-like heteroaromatic compounds to be synthesized without difficulty.     

15N NMR chemical shifts for the identification of dipyrrolic structures

A variety of dipyrromethanes and dipyrromethenes have been prepared, and their 15N NMR chemical shifts have been measured by two-dimensional correlation to 1H NMR signals. The nitrogen atoms in five examples of dipyrromethanes consistently exhibit chemical shifts around -231 ppm, relative to nitromethane. Seven examples of hydrobromide salts of meso-unsubstituted dipyrromethenes consistently display 15N chemical shifts around -210 ppm, while their corresponding zinc(II) complexes exhibit chemical shifts around -170 ppm. The presence of electron-withdrawing substituents on one of the pyrrolic rings of dipyrromethenes affects the chemical shifts of both of the nitrogen nuclei in the molecule. Boron difluoride complexes of meso-unsubstituted dipyrromethenes display 15N chemical shifts around -190 ppm. Two examples of free-base dipyrromethenes bearing substituents at the meso-position exhibit 15N chemical shifts at approximately -156 ppm, and for the zinc complexes of these compounds at -162 ppm. One-bond nitrogen-hydrogen coupling constants, when measurable, were consistently in the range of -96 Hz. Since the measured 15N chemical shifts have such a high regularity correlated to structure, they can be used as diagnostic indications for identifying the structure of dipyrrolic compounds.