Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species

Investigation of the dependence of product enantiometric excess (ee) on catalyst ee is a widely used tool to probe the mechanism of an enantioselective reaction; in particular, the observation of a nonlinear relationship is usually interpreted as an indication of the presence of one or more species that contain at least two units of the chiral entity. In this report, we demonstrate that catalytic enantioconvergent reactions can display an intrinsic negative nonlinear effect that originates purely from the kinetic characteristics of certain enantioconvergent processes and is independent of possible aggregation of the chiral entity. Specifically, this intrinsic negative nonlinear effect can arise when there is a kinetic resolution of the racemic starting material, and its magnitude is correlated with the selectivity factor and the conversion; the dependence on conversion provides a ready means to distinguish it from a more conventional nonlinear effect. We support our analysis with experimental data for two distinct enantioconvergent processes, one catalyzed by a chiral phosphine and the other by a chiral Pd/phosphine complex

Rapid climate change results in long-lasting spatial homogenization of phylogenetic diversity

Scientific understanding of biodiversity dynamics, resulting from past climate oscillations and projections of future changes in biodiversity, has advanced over the past decade. Little is known about how these responses, past or future, are spatially connected. Analyzing the spatial variability in biodiversity provides insight into how climate change affects the accumulation of diversity across space. Here, we evaluate the spatial variation of phylogenetic diversity of European seed plants among neighboring sites and assess the effects of past rapid climate changes during the Quaternary on these patterns. Our work shows a marked homogenization in phylogenetic diversity across Central and Northern Europe linked to high climate change velocity and large distances to refugia. Our results suggest that the future projected loss in evolutionary heritage may be even more dramatic, as homogenization in response to rapid climate change has occurred among sites across large landscapes, leaving a legacy that has lasted for millennia

Disentangling the processes driving plant assemblages in mountain grasslands across spatial scales and environmental gradients

1. Habitat filtering and limiting similarity are well-documented ecological assembly processes that hierarchically filter species across spatial scales, from a regional pool to local assemblages. However, information on the effects of fine-scale spatial partitioning of species, working as an additional mechanism of coexistence, on community patterns, is much scarcer. 2. In this study, we quantified the importance of fine-scale spatial partitioning, relative to habitat filtering and limiting similarity, in structuring grassland communities in the western Swiss Alps. To do so, 298 vegetation plots (2 m × 2 m ) each with five nested subplots (20 cm × 20 cm) were used for trait based assembly tests (i.e. comparisons with several alternative null expectations), examining the observed plot and subplot level α-diversity (indicating habitat filtering and limiting similarity) and the between-subplot β-diversity of traits (indicating fine-scale spatial partitioning). We further assessed variations in the detected signatures of these assembly processes along a set of environmental gradients. 3. We found habitat filtering to be the dominating assembly process at the plot level with diminished effect at the subplot level, while limiting similarity prevailed at the subplot level with weaker average effect at the plot level. Plot-level limiting similarity was positively correlated with fine-scale partitioning suggesting that the trait divergence may result from a combination of competitive exclusion between functionally similar species and environmental micro-heterogeneities. Overall, signatures of assembly processes only marginally changed along environmental gradients but the observed trends were more prominent at the plot than at the subplot scale. Synthesis: Our study emphasises the importance of considering multiple assembly processes and traits simultaneously across spatial scales and environmental gradients to understand the complex drivers of plant community composition

Blue and green food webs respond differently to elevation and land use.

While aquatic (blue) and terrestrial (green) food webs are parts of the same landscape, it remains unclear whether they respond similarly to shared environmental gradients. We use empirical community data from hundreds of sites across Switzerland and a synthesis of interaction information in the form of a metaweb to show that inferred blue and green food webs have different structural and ecological properties along elevation and among various land-use types. Specifically, in green food webs, their modular structure increases with elevation and the overlap of consumers' diet niche decreases, while the opposite pattern is observed in blue food webs. Such differences between blue and green food webs are particularly pronounced in farmland-dominated habitats, indicating that anthropogenic habitat modification modulates the climatic effects on food webs but differently in blue versus green systems. These findings indicate general structural differences between blue and green food webs and suggest their potential divergent future alterations through land-use or climatic changes

Blue and green food webs respond differently to elevation and land use

While aquatic (blue) and terrestrial (green) food webs are parts of the same landscape, it remains unclear whether they respond similarly to shared environmental gradients. We use empirical community data from hundreds of sites across Switzerland and a synthesis of interaction information in the form of a metaweb to show that inferred blue and green food webs have different structural and ecological properties along elevation and among various land-use types. Specifically, in green food webs, their modular structure increases with elevation and the overlap of consumers’ diet niche decreases, while the opposite pattern is observed in blue food webs. Such differences between blue and green food webs are particularly pronounced in farmland-dominated habitats, indicating that anthropogenic habitat modification modulates the climatic effects on food webs but differently in blue versus green systems. These findings indicate general structural differences between blue and green food webs and suggest their potential divergent future alterations through land-use or climatic changes

Dimerization of functional pyrroloindolizines for the synthesis of complex myrmicarin alkaloids

The union of functionalized pyrroloindolizines for the synthesis of heterodimeric products relevant to myrmicarin alkaloids is described. Design and synthesis of tricyclic substrates and new methods for their union enable the investigation of late-stage cyclopentannulation strategies. The rapid assembly of dimeric structures using unique modes of pyrroloindolizine reactivity presents a concise approach to the dimeric myrmicarins and relevant derivatives.National Institutes of Health (U.S.) (NIH-NIGMS (GM074825))Alfred P. Sloan Foundation (Research Fellowship)Henry & Camille Dreyfus Foundation (Teacher-Scholar)Novartis (Firm) (Graduate Fellowship

The diastereoselective Meth-Cohn epoxidation of camphor-derived vinyl sulfones

Some camphor-derived vinyl sulfones bearing oxygen functionality at the allylic position have been synthesized and their nucleophilic epoxidation reactions under Meth-Cohn conditions have been explored. The γ-oxygenated camphor-derived vinyl sulfones underwent mildly diastereoselective nucleophilic epoxidation reactions, affording the derived sulfonyloxiranes in up to 5.8:1 dr. The observed diastereoselectivities were sensitive to the reaction conditions employed. In contrast, no stereoselectivity was observed in the nucleophilic epoxidation of the corresponding γ-oxygenated isobornyl vinyl sulfone. A tentative mechanism has been proposed to explain the origins of the diastereoselectivit