A chiral phosphazane reagent strategy for the determination of enantiomeric excess of amines

Methods for measuring enantiomeric excess (ee) of organic molecules by NMR spectroscopy provide rapid analysis using a standard technique that is readily available. Commonly this is accomplished by chiral derivatisation of the detector molecule (producing a chiral derivatisation agent, CDA), which is reacted with the mixture of enantiomers under investigation. However, these CDAs have almost exclusively been based on carbon frameworks, which are generally costly and/or difficult to prepare. In this work, a methodology based on the readily prepared inorganic cyclodiphosph(iii)azane CDA ClP(μ-N^tBu)₂POBorn (Born = endo-(1S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl) is shown to be highly effective in the measurement of ee’s of chiral amines, involving in situ reaction of the chiral amines (R*NH₂) with the P–Cl bond of the CDA followed by quaternization of the phosphorus framework with methyl iodide. This results in sharp ³¹P NMR signals with distinct chemical shift differences between the diastereomers that are formed, which can be used to obtain the ee directly by integration. Spectroscopic, X-ray structural and DFT studies suggest that the NMR chemical shift differences between diastereomers is steric in origin, with the sharpness of these signals resulting from conformational locking of the bornyl group relative to the P₂N₂ ring induced by the presence of the P(v)-bonded amino group (R*NH). This study showcases cheap inorganic phosphazane CDAs as simple alternatives to organic variants for the rapid determination of ee.

The simple inorganic cyclodiphosph(iii)azane chiral derivatisation agent ClP(μ-^tBuN)₂POBorn (Born = endo-(1S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl) is shown to be effective in the measurement of ee’s of chiral amines using ³¹P NMR spectroscopy.     

Clustering patterns in high-energy hadron collisions

The event-to-event fluctuations of the rapidity distributions are analyzed for semi-inclusive data obtained from 205 GeV/c and 303 GeV/c proton-proton collisions observed at NAL. The results indicate the presence of clustering effects, with cluster sizes approximating those observed in the quasi-elastic events. The average cluster size appears to be independent of the multiplicity of the final state.     

Delayed neutrons and high-energy γ-rays from decay of 87Br

Delayed neutrons and high-energy γ-rays following decay of ⁸⁷Br have been studied to characterize the β-decay to and the decay of neutron unbound levels in ⁸⁷Kr. The principal part of the neutron spectrum appears due to some 20–30 individual transitions and for seven of these, decay by γ-ray emission has been demonstrated. The β-strength function derived from these data and the decay scheme at lower energies is dominated by a broad resonance located near the neutron binding energy which can be identified with the main strength of a single-particle transition. The fluctuations in the reduced β-transition probabilities are found to be in accord with the Porter-Thomas distribution and the observed level density just above the neutron binding energy is consistent with the Gilbert and Cameron prediction after accounting for fluctuation in the β-decay transition probabilities.