Choosing and using climate-change scenarios for ecological-impact assessments and conservation decisions.

Increased concern over climate change is demonstrated by the many efforts to assess climate effects and develop adaptation strategies. Scientists, resource managers, and decision makers are increasingly expected to use climate information, but they struggle with its uncertainty. With the current proliferation of climate simulations and downscaling methods, scientifically credible strategies for selecting a subset for analysis and decision making are needed. Drawing on a rich literature in climate science and impact assessment and on experience working with natural resource scientists and decision makers, we devised guidelines for choosing climate-change scenarios for ecological impact assessment that recognize irreducible uncertainty in climate projections and address common misconceptions about this uncertainty. This approach involves identifying primary local climate drivers by climate sensitivity of the biological system of interest; determining appropriate sources of information for future changes in those drivers; considering how well processes controlling local climate are spatially resolved; and selecting scenarios based on considering observed emission trends, relative importance of natural climate variability, and risk tolerance and time horizon of the associated decision. The most appropriate scenarios for a particular analysis will not necessarily be the most appropriate for another due to differences in local climate drivers, biophysical linkages to climate, decision characteristics, and how well a model simulates the climate parameters and processes of interest. Given these complexities, we recommend interaction among climate scientists, natural and physical scientists, and decision makers throughout the process of choosing and using climate-change scenarios for ecological impact assessment. Selección y Uso de Escenarios de Cambio Climático para Estudios de Impacto Ecológico y Decisiones de Conservación.

Stereochemistry of 1,2-elimination reactions at the E2-E1cB interface--tert-butyl 3-tosyloxybutanoate and its thioester.

Experimental data on the stereoselectivity of base-catalyzed 1,2-elimination reactions that produce conjugated carbonyl compounds are scarce in spite of the importance of these reactions in organic and biochemistry. As part of a comprehensive study in this area, we have synthesized stereospecifically-deuterated beta-tosyloxybutanoate esters and thioesters and studied the stereoselectivity of their elimination reactions under non-ion pairing conditions. With the availability of both the (2R*,3R*) and (2R*,3S*) diastereomers the innate stereoselectivity could be determined unambiguously. (1)H and (2)H NMR data show that these substrates produce 5-6% syn elimination, the usual amount for acyclic substrates undergoing E2 reactions. Contrary to earlier suggestions, activation by a carbonyl group has virtually no influence upon the stereoselectivity. Elimination of the (2R*,3R*) diastereomer of the beta-tosyloxyester and thioester produces 21-25% of the (Z)-alkene, much more than observed with a poorer beta-nucleofuge. A relatively large amount of (Z)-alkene product seems to be a good marker for an E2 pathway, in which the transition state is E1cB-like, rather than an E1cB(irrev) mechanism. Syn KIE values were higher than those for anti elimination for the esters as well as the thioesters. Experimental challenges to the synthesis of stereospecifically-deuterated beta-tosyloxyesters are discussed.