Enantioselective Intramolecular Michael Addition of Nitronates onto Conjugated Esters: Access to Cyclic γ-Amino Acids with up to Three Stereocenters

A highly stereoselective synthesis of conformationally constrained cyclic γ-amino acids has been devised. The key step involves an intramolecular cyclization of a nitronate onto a conjugated ester, promoted by a bifunctional thiourea catalyst. This methodology has been successfully applied to generate a variety of γ-amino acids, including some containing three contiguous stereocenters, with very high diastereoselectivity and excellent enantioselectivity. It is postulated that an interaction that is key to the success of the process is the simultaneous coordination of the thiourea functionality to both the conjugated ester and the nitronate. Finally, the synthetic utility of these compounds is demonstrated in the synthesis of two dipeptides derived from the C- and N-termini.

Current changes in tropical precipitation

Current changes in tropical precipitation from satellite data and climate models are assessed. Wet and dry regions of the tropics are defined as the highest 30% and lowest 70% of monthly precipitation values. Observed tropical ocean trends in the wet regime (1.8%/decade) and the dry regions (−2.6%/decade) according to the Global Precipitation Climatology Project (GPCP) over the period including Special Sensor Microwave Imager (SSM/I) data (1988–2008), where GPCP is believed to be more reliable, are of smaller magnitude than when including the entire time series (1979–2008) and closer to model simulations than previous comparisons. Analysing changes in extreme precipitation using daily data within the wet regions, an increase in the frequency of the heaviest 6% of events with warming for the SSM/I observations and model ensemble mean is identified. The SSM/I data indicate an increased frequency of the heaviest events with warming, several times larger than the expected Clausius–Clapeyron scaling and at the upper limit of the substantial range in responses in the model simulations.

General concepts in meteorology and dynamics

The aim of this chapter is to give a general overview of the atmospheric circulation, highlighting the main concepts that are important for a basic understanding of meteorology and atmospheric dynamics relevant to atmospheric data assimilation.