Synthesis of tylocrebrine and related phenanthroindolizidines by VOF3-mediated oxidative aryl-alkene coupling

A highly convergent strategy to prepare phenanthroindolizidines is reported involving three consecutive C-C coupling reactions. This sequence features a novel VOF(3)-mediated aryl-alkene coupling in the final step, which enables regioselective preparation of C5-substituted phenanthroindolizidines for the first time. This strategy has been applied to the synthesis of eight natural and unnatural members in this class to investigate the scope of this chemistry and to explore structure-activity relationships.     

Three-component synthesis of cyclic enaminones via ketene cyclization

Cyclic six-membered enaminones were synthesized from three components (bromodiazoacetone, primary amine, and alkyne) in high yields via aza-Michael addition, Wolff rearrangement, and nucleophilic ketene cyclization.     

Palladium(II)-catalyzed dehydrogenative alkenylation of cyclic enaminones via the Fujiwara-Moritani reaction

A new Pd(II)-catalyzed dehydrogenative alkenylation reaction involving two alkenes was developed. A variety of nonaromatic, cyclic enaminones were successfully coupled to primary and secondary alkenes yielding a series of unique 1,3-dienes. The generality of this transformation presents a useful strategy for directly cross-coupling alkenes and offers an attractive new approach to functionalize enaminones.     

Crushing effects on TL and OSL on quartz: relevance to fault dating

The effect of crushing on the TL and OSL signals in quartz was investigated to examine the feasibility of using OSL and TL for dating of faulted rocks. 275°C TL signals were not reduced by crushing by hand (mortar and pestle), in a pellet die press, or using an automatic mortar and pestle, but the sensitivity of the 100°C TL signal to a test dose decreased in crushed samples. Green light-stimulated OSL signal intensities were not decreased after crushing, but showed strongly increased inter-aliquot variability after crushing. We concluded that OSL and TL in quartz might be useful to characterize the crushing history of quartz in fault rocks, but their usefulness in dating fault events was not evident because we did not find evidence of signal zeroing under the conditions used in this study.     

Spezielle Translationsebenen und ihre Homomorphismen

Ohne Zusammenfassung     

Mild and selective hydrozirconation of amides to aldehydes using Cp2Zr(H)Cl: scope and mechanistic insight

An investigation of the use of Cp2Zr(H)Cl (Schwartz's reagent) to reduce a variety of amides to the corresponding aldehydes under very mild reaction conditions and in high yields is reported. A range of tertiary amides, including Weinreb's amides, can be converted directly to the corresponding aldehydes with remarkable chemoselectivity. Primary and secondary amides proved to be viable substrates for reduction as well, although the yields were somewhat diminished as compared to the corresponding tertiary amides. Results from NMR experiments suggested the presence of a stable, 18-electron zirconacycle intermediate that presumably affords the aldehyde upon water or silica gel workup. A series of competition experiments revealed a preference of the reagent for substrates in which the lone pair of the nitrogen is electron releasing and thus more delocalized across the amide bond by resonance. This trend accounts for the observed excellent selectivity for tertiary amides versus esters. Experiments regarding the solvent dependence of the reaction suggested a kinetic profile similar to that postulated for the hydrozirconation of alkenes and alkynes. Addition of p-anisidine to the reaction intermediate resulted in the formation of the corresponding imine mimicking the addition of water that forms the aldehyde.     

Supramolecular polymers based on the quadruplex formation of ditopic guanosine macromonomers in nonaqueous media

The formation of supramolecular polymeric aggregates with a molecular mass of 100 kDa in a nonaqueous solution from a telechelic dimer of isopropylidene guanosine in the presence of K(+) ions is reported. The possible structure of macromonomers resulting from the development of G4 quartets was deduced from DOSY NMR, circular dichroism spectra, and dynamic light scattering measurements.     

A simplification of the double-sweep algorithm to solve the k-shortest path problem

In this paper, we define the k-shortest path problem, which will be used to model the problem of routing aircraft through a network of airfields. This problem finds the optimal alternative routes from one or more origins to one or more destinations. We solve this problem using the double-sweep algorithm. We present a simplification to the double-sweep algorithm, and show that this simplification reduces the computational complexity of the algorithm by a factor of k. We prove that the simplified double-sweep algorithm converges. Finally, we demonstrate this algorithm on a small airlift network.     

Analytical solutions for a class of nonlinear differential equations using altran

What follows is a discussion on the application of a digital computer to solve analytically a class of nonlinear ordinary differential equations. The asymptotic method of Krylov, Bogoliubov and Mitropolsky is employed to obtain analytical solutions. In addition, a procedure has been developed through which the initial amplitude and phase can be expressed as functions of initial displacement and velocity without the need of integration. Since the algorithms are analytical in nature, the truncated power series capability of the symbolic algebraic system ALTRAN has been used to generate analytical solutions automatically.