Bakers' Yeast Reduction of γ and δ Ketonitriles: Intermediates for the Synthesis of (S)-5-Hexanolide and Other Chiral Lactones

Abstract

A number of γ and δ ketonitriles have been synthesized and their reduction with bakers yeast carefully studied. Both 4-oxopentanenitrile and 5-oxohexanenitrile are reduced in moderate yields to the corresponding (S) alcohols of high ee while other substrates gave products of varying optical purities. These alcohols are useful intermediates for the preparation of chiral lactones, including the synthetically important (S)(?)-4-methylbutyrolactone and (S)-(?)-5-hexanolide.     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Generalized ray expansion for pulse propagation and attenuation in fluid-saturated porous media

A theory suitable for studying pulses propagating through a layered fluid-saturated porous medium is presented. Biot's theory is used to describe the constitutive equation of a fluid-saturated porous solid. Since fast and slow compressional waves exist in a Biot solid even at normal incidence, there is mode conversion at the interface and, therefore, the transmission and reflection coefficients are 2x2 matrices. We use matrix methods in developing the solution of the wave propagation problem. A generalized ray expansion algorithm is obtained by using the Gauss-Seidel matrix iterative method. The arrivals of the fast and the slow waves are easily identified. A compact computational algorithm is developed using combinatorial analysis and the Cayley-Hamilton theorem.     

Measurement at the field scale of soil δ13C and δ15N under improved grassland

Variations in natural abundance of carbon (C) and nitrogen (N) stable isotopes are widely used as tools for many aspects of scientific research. By examining variations in the ratios of heavy to light stable isotopes, information can be obtained as to what physical, chemical and biological processes may be occurring. The spatial heterogeneity of soil δ¹⁵N‐ and δ¹³C‐values across a range of scales and under different land use have been described by a number of researchers and the natural abundances of the C and N stable isotopes in soils have been found to be correlated with many factors including hydrology, topography, land use, vegetation cover and climate. In this study the Latin square sampling +1 (LSS+1) sampling method was compared with a simple grid sampling approach for δ¹³C and δ¹⁵N measurement at the field scale. A set of 144 samples was collected and analysed for δ¹⁵N and δ¹³C from a 12 × 12 grid (in a 1 ha improved grassland field in south‐west England). The dimension of each cell of the grid was approximately 11 × 6 m. The 12 × 12 grid was divided into four 6 × 6 grids and the LSS+1 sampling technique was applied to these and the main 12 × 12 grid for a comparison of sample means and variation. The LSS+1 means from the 12 × 12 grid and the four 6 × 6 grids compared well with the overall grid mean because of the low variation within the field. The LSS+1 strategy (13 samples) generated representative samples from the 12 × 12 grid, and hence would be an acceptable method for sampling similar plots for the measurement of mean isotopic composition. Copyright © 2010 John Wiley & Sons, Ltd.     

Reactivity of N-nitrosoamides in confined spaces

The thermal rearrangement of several N-nitrosoamides was studied by ¹H NMR in the context of reversible encapsulation. The N-nitrosoamide guests were isolated from the bulk solvent in a hydrogen-bonded dimeric host capsule which prevented their rearrangement. The guests appear to be preserved in their ground state conformations by the pressure exerted by the host. The conformations of the free and bound N-nitrosoamides are of comparable relative energies as determined by DFT calculations.