Regio- and diastereoselective boron-mediated aldol reactions of chiral α,β,γ,δ-unsaturated N-acyloxazolidinones

Chiral N-acyloxazolidinones derived from conjugated dienoic acids undergo boron-mediated aldol condensation in good yield and with high regio- and diastereoselectivity to provide a convenient method for introducing a 1,3-diene subunit. The condensation of a homologous triene derivative is also described.     

Electrochemical processes in electrospray ionization mass spectrometry

Editorial Comment Last month we presented, as a Special Feature, a set of five articles that constituted a Commentary on the fundamentals and mechanism of electrospray ionization (ESI). These articles produced some lively discussion among the authors on the role of electrochemistry in ESI. Six authors participated in a detailed exchange of views on this topic, the final results of which constitute this month's Special Feature. We particularly hope that younger scientists will find value in this month's Special Feature, not only for the science that it teaches but also what it reveals about the processes by which scientific conclusions are drawn. To a degree, the contributions part the curtains on these processes and show science in action. We sincerely thank the contributors to this discussion. The give and take of intellectual debate is not always easy, and to a remarkable extent this set of authors has maintained good humor and friendships, even when disagreeing strongly on substance. Graham Cooks and Richard Caprioli Copyright 2000 John Wiley & Sons, Ltd.     

Derivatization for electrospray ionization-mass spectrometry. 4. Alkenes and alkynes

A survey of derivatization strategies and prospective derivatization reactions for conversion of simple alkenes and alkynes to 'electrospray-active' species is presented. General synthetic strategies are discussed and illustrative examples of prospective derivatives prepared from model compounds are presented along with their electrospray ionization (ES) mass spectra. The identified derivatives of these neutral, nonpolar analytes are either ionic or are ionizable in solution through Bronsted acid/base chemistry, by Lewis acid/base chemistry, or by chemical or electrochemical electron-transfer chemistry. Once ionized, the derivatives are expected to be amenable to detection by electrospray ionization-mass spectrometry. Derivatives are identified for positive and negative ion analysis of both alkenes and alkynes. Copyright 2000 John Wiley & Sons, Ltd.     

Asymmetric catalysis using self-assembled chiral bidentate P,P-ligands

A strategy is described for modular catalyst development based upon metal-directed self-assembly of bifunctional subunits around a structural metal to form a heteroleptic complex in which a second set of ligating groups are now suitably disposed to bind a second metal to form a catalytic site. A library of chiral diphosphites was prepared via metal-directed self-assembly and used in a simple asymmetric allylic amination, giving enantiomeric excesses as high as 97%.     

More Randomness of Environment Does Not Always Slow Down a Random Walk

We consider a random walk on in a stationary and ergodic random environment, whose states are called types of the vertices of . We find conditions for which the speed of the random walk is positive. In the case of a Markov chain environment with finitely many states, we give an explicit formula for the speed and for the asymptotic proportion of time spent at vertices of a certain type. Using these results, we compare the speed of random walks on in environments of varying randomness.     

Novel motifs for magnetic exchange interactions as exemplified in one dimensional magnets based on the FeCl3-α-di-imine system: Nuclear gamma resonance evidence of slow paramagnetic relaxation and 3D-ordering

The extremes of single ion slow paramagnetic relaxation and cooperative 3D-antiferromagnetic order are exemplified in a series of structurally characterized complexes based on the anhydrous FeCl₃-α-di-imine system. “Soft” Cl−Cl contacts, C−C (π-π) and hydrogen bonding interactions are found to lead to surprisingly strong magnetic exchange among five and six coordinate high-spin iron III monomers. The latter form the building blocks of novel “double chain” polymer magnets held together via the preceding “weak” interactions.     

Biased random walks on directed trees

Summary. We define directed rooted labeled and unlabeled trees and find measures on the space of directed rooted unlabeled trees which are invariant with respect to transition probabilities corresponding to a biased random walk on a directed rooted labeled tree. We use these to calculate the speed of a biased random walk on directed rooted labeled trees. The results are mainly applied to directed trees with recurrent subtrees, where the random walker cannot escape. Received: 12 March 1997/ In revised form: 11 December 1997     

Catalytic asymmetric hydroboration of β,γ-unsaturated Weinreb amides: striking influence of the borane

Subtle differences in the structure of the borane strongly influence the catalytic efficiency and level of enantioselectivity in the catalytic asymmetric hydroboration of β,γ-unsaturated Weinreb amides.     

Enhancing Fullerene‐Based Solar Cell Lifetimes by Addition of a Fullerene Dumbbell

Cost‐effective, solution‐processable organic photovoltaics (OPV) present an interesting alternative to inorganic silicon‐based solar cells. However, one of the major remaining challenges of OPV devices is their lack of long‐term operational stability, especially at elevated temperatures. The synthesis of a fullerene dumbbell and its use as an additive in the active layer of a PCDTBT:PCBM‐based OPV device is reported. The addition of only 20 % of this novel fullerene not only leads to improved device efficiencies, but more importantly also to a dramatic increase in morphological stability under simulated operating conditions. Dynamic secondary ion mass spectrometry (DSIMS) and TEM are used, amongst other techniques, to elucidate the origins of the improved morphological stability.