Cascade iminium ion reactions for the facile synthesis of quinolizidines. Concise syntheses of (+/-)-epilupinine and (-)-epimyrtine

Several novel cascade processes have been designed and developed that involve sequential reactions of imines and iminium ions to form substituted quinolizidine ring systems in a single step from simple and readily available starting materials. The utility and promise of these cascade reactions is evident from their application to extraordinarily concise syntheses of the representative quinolizidine alkaloids (+/-)-epilupinine and (-)-epimyrtine.     

Morphanthridines III. 6-Basic substituted morphanthridines

The reaction of hydrazines and amines with 6-chloromorphanthridine was investigated. Grignard coupling of aminoalkyl halides with 6-chloromorphanthridine afforded 6-amino-alkylmorphanthridines. Cyclization of 6-(2-chloroethylamino)morphanthridine yielded the new ring system 5′H-imidazo[5, 6-a]dibenz[b, ejazepine, which was aminoalkylated by generation of the 11-position anion with butyllithium, followed by treatment with a tertiary aminoalkyl halide.     

Microwave assisted digestion of atmospheric aerosol samples followed by inductively coupled plasma mass spectrometry determination of trace elements

A microwave digestion method in a closed vessel was developed for the determination of trace metals in atmospheric aerosols using inductively coupled plasma mass spectrometry (ICP-MS). A recovery study for the elements V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Sb, and Pb was conducted using multi-elemental standard solutions, NIST 1633b Trace Elements in Coal Fly Ash, and NIST 1648 Urban Particulate Matter. A simple digestion method using only HNO₃/H₂O₂ gave good recoveries (90%–108%) for all elements except Cr in SRM 1648, but yielded low recoveries for SRM 1633b. A more robust method using HNO₃/H₂O₂/HF/H₃BO₃ yielded higher recoveries (82%–¶103%) for the lighter elements (V – Zn) in SRM 1633b, and improved the Cr recovery in SRM 1648, but decreased the Se recovery in both SRMs. A comparative analysis of aerosol samples obtained at a remote mountain location Nathiagali, Pakistan (2.5 km above mean sea level), and Mayville, New York, downwind from the highly industrialized Midwestern United States, was carried out using Instrumental Neutron Activation Analysis (INAA) for the elements Cr, Mn, Fe, Co, Zn, As, Se, and Sb. The simple digestion method yielded excellent agreement for Cr, Fe, Zn, As, Se, and Sb, with slopes of the ICP-MS vs. INAA regressions of 0.90–1.00 and R² values of 0.96–1.00. The regressions for Mn and Co had slopes of 0.82 and 0.84 with R² values of 0.83 and 0.82, respectively. Addition of HF/H₃BO₃ did not improve the correlation for any of the elements and degraded the precision somewhat. The technique provides sensitivity and accuracy for trace elements in relatively small aerosol samples used in atmospheric chemistry studies related to SO₂ oxidation in cloud droplets. The ability to determine concentrations of a very large number of elements from a single analysis will permit source apportionment of various trace pollutants and hence strategies to control the sources of air pollution. This is particularly important as the health effects of particulate matter are increasingly recognized.     

Remote control of diastereoselectivity in intramolecular reactions of chiral allylsilanes

During investigations of cyclization reactions between chiral allylsilanes and N-acyliminium ions, it was discovered that a suitably positioned benzyloxy group on the allylsilane component caused a reversal in the diastereoselectivity of these reactions relative to that normally observed with alkyl-substituted allylsilanes. This effect was subsequently observed in two other reaction types. Investigations into this effect led to the proposal of product formation through thermodynamic control facilitated by neighboring group interactions with a transient cationic species. This hypothesis was experimentally supported by the isolation of an intermediate in the proposed mechanistic pathway.     

Structure determination of mycolactone C via total synthesis

[structure: see text] By total synthesis, mycolactone C has been established as an approximately 1:1 mixture of Z-Delta4'5'- and E-Delta4'5'-geometric isomers of C12'-deoxymycolactones A and B.     

The thermal decomposition of calcium,sodium, silver and copper(II) acetates

The thermal decomposition of the acetates of calcium, sodium, silver and copper(II) have been investigated using thermogravimetry and differential thermal analysis, together with analysis of the gaseous products formed during the decomposition process. The results indicate that the major organic product formed is either acetone or acetic acid, depending on whether the final solid product is the oxide or the metal.     

Embedding as a modeling problem

Standard approaches to time-delay embedding will often fail to provide an embedding that is useful for many common applications. This happens in particular when there are multiple timescales in the dynamics. We present a modified procedure, non-uniform embedding, which overcomes such problems in many cases. For more complex nonlinear dynamics we introduce variable embedding, where, in a suitable sense, the embedding changes with the state of the system. We show how to implement these procedures by combining embedding and modeling into a single procedure with a single optimization goal.