Aza-Quasi-Favorskii Reaction: Construction of Highly Substituted Aziridines through a Concerted Multibond Rearrangement Process.

A new molecular rearrangement, the aza-Quasi-Favorskii rearrangement, has been developed for the construction of highly substituted aziridines. Electron-deficient O-sulfonyl oximes react readily with α,α-disubstituted acetophenone-derived enolates to furnish highly substituted aziridines via this unprecedented domino process. In-depth computational studies reveal an asynchronous yet concerted nitrenoid-type rearrangement pathway.

What does a threatened saproxylic beetle look like? Modelling extinction risk using a new morphological trait database.

The extinction of species is a non-random process, and understanding why some species are more likely to go extinct than others is critical for conservation efforts. Functional trait-based approaches offer a promising tool to achieve this goal. In forests, deadwood-dependent (saproxylic) beetles comprise a major part of threatened species, but analyses of their extinction risk have been hindered by the availability of suitable morphological traits. To better understand the mechanisms underlying extinction in insects, we investigated the relationships between morphological features and the extinction risk of saproxylic beetles. Specifically, we hypothesised that species darker in colour, with a larger and rounder body, a lower mobility, lower sensory perception and more robust mandibles are at higher risk. We first developed a protocol for morphological trait measurements and present a database of 37 traits for 1,157 European saproxylic beetle species. Based on 13 selected, independent traits characterising aspects of colour, body shape, locomotion, sensory perception and foraging, we used a proportional-odds multiple linear mixed-effects model to model the German Red List categories of 744 species as an ordinal index of extinction risk. Six out of 13 traits correlated significantly with extinction risk. Larger species as well as species with a broad and round body had a higher extinction risk than small, slim and flattened species. Species with short wings had a higher extinction risk than those with long wings. On the contrary, extinction risk increased with decreasing wing load and with higher mandibular aspect ratio (shorter and more robust mandibles). Our study provides new insights into how morphological traits, beyond the widely used body size, determine the extinction risk of saproxylic beetles. Moreover, our approach shows that the morphological characteristics of beetles can be comprehensively represented by a selection of 13 traits. We recommend them as a starting point for functional analyses in the rapidly growing field of ecological and conservation studies of deadwood.

Intramolecular N-Me and N-H aminoetherification for the synthesis of N-unprotected 3-amino-O-heterocycles.

A mild Rh-catalyzed method for synthesis of cyclic unprotected N-Me and N-H 2,3-aminoethers using an olefin aziridination-aziridine ring-opening domino reaction has been developed. The method is readily applicable to the stereocontrolled synthesis of a variety of 2,3-disubstituted aminoether O-heterocyclic scaffolds, including tetrahydrofurans, tetrahydropyrans and chromanes.

Synthesis of (±)-Setigerumine†I: Biosynthetic Origins of the Elusive Racemic Papaveraceae Isoxazolidine Alkaloids*.

The biosynthetic origins of the structurally related racemic isoxazolidine Papaveraceae alkaloids Setigerumine I, Dactylicapnosinine and Dactylicapnosine have remained elusive since their original isolation over two decades ago. Herein we report the first biosynthetic hypothesis for their formation and, inspired by it, the first synthesis of (±)-Setigerumine I with accompanying computational rationale. Based on the results, these isoxazolidine alkaloids arise from racemizing oxidative rearrangements of prominent isoquinoline alkaloids Noscapine and Hydrastine. The key steps featured in this synthesis are a room temperature Cope elimination and a domino oxidation/inverse-electron demand 1,3-dipolar cycloaddition of an axially chiral, yet configurationally unstable, intermediate. The work opens this previously inaccessible family of natural products for biological studies.

Total synthesis of isatindigotindoline C.

Total synthesis of isatindigotindoline C, a 3,3'-spiropyrrolidine oxindole alkaloid, is achieved in two steps using an exo-selective decarboxylative 1,3-dipolar cycloaddition as the key step. The synthesis verifies the originally assigned relative anti-stereochemistry for the bis-oxindole core of isatindigotindoline C.

Formal Synthesis of ent-Cephalotaxine Using a One-Pot Parham-Aldol Sequence.

A short formal synthesis of ent-Cephalotaxine is achieved. The approach features a new Lewis acid-mediated [2,3]-Stevens rearrangement of N-allylated prolineamide to generate a key quaternary stereogenic center. Additionally, a one-pot Parham-aldol sequence was developed to rapidly assemble two of the four rings in the cephalotaxine core.

Alternative measures of trait-niche relationships: A test on dispersal traits in saproxylic beetles.

Functional trait approaches are common in ecology, but a lack of clear hypotheses on how traits relate to environmental gradients (i.e., trait-niche relationships) often makes uncovering mechanisms difficult. Furthermore, measures of community functional structure differ in their implications, yet inferences are seldom compared among metrics. Community-weighted mean trait values (CWMs), a common measure, are largely driven by the most common species and thus do not reflect community-wide trait-niche relationships per se. Alternatively, trait-niche relationships can be estimated across a larger group of species using hierarchical joint species distribution models (JSDMs), quantified by a parameter Γ. We investigated how inferences about trait-niche relationships are affected by the choice of metric. Using deadwood-dependent (saproxylic) beetles in fragmented Finnish forests, we followed a protocol for investigating trait-niche relationships by (1) identifying environmental filters (climate, forest age, and deadwood volume), (2) relating these to an ecological function (dispersal ability), and (3) identifying traits related to this function (wing morphology). We tested 18 hypothesized dispersal relationships using both CWM and Γ estimates across these environmental gradients. CWMs were more likely than Γ to show support for trait-niche relationships. Up to 13% of species' realized niches were explained by dispersal traits, but the directions of effects were consistent with fewer than 11%-39% of our 18 trait-niche hypotheses (depending on the metric used). This highlights the difficulty in connecting morphological traits and ecological functions in insects, despite the clear conceptual link between landscape connectivity and flight-related traits. Caution is thus warranted in hypothesis development, particularly where apparent trait-function links are less clear. Inferences differ when CWMs versus Γ estimates are used, necessitating the choice of a metric that reflects study questions. CWMs help explain the effects of environmental gradients on community trait composition, whereas the effects of traits on species' niches are better estimated using hierarchical JSDMs.

Modeling species co-occurrence by multivariate logistic regression generates new hypotheses on fungal interactions.

Signals of species interactions can be inferred from survey data by asking if some species occur more or less often together than what would be expected by random, or more generally, if any structural aspect of the community deviates from that expected from a set of independent species. However, a positive (or negative) association between two species does not necessarily signify a direct or indirect interaction, as it can result simply from the species having similar (or dissimilar) habitat requirements. We show how these two factors can be separated by multivariate logistic regression, with the regression part accounting for species-specific habitat requirements, and a correlation matrix for the positive or negative residual associations. We parameterize the model using Bayesian inference with data on 22 species of wood-decaying fungi acquired in 14 dissimilar forest sites. Our analyses reveal that some of the species commonly found to occur together in the same logs are likely to do so merely by similar habitat requirements, whereas other species combinations are systematically either over- or underrepresented also or only after accounting for the habitat requirements. We use our results to derive hypotheses on species interactions that can be tested in future experimental work.

Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones.

A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions.

Arylboronic Acid-Catalyzed C-Allylation of Unprotected Oximes: Total Synthesis of N-Me-Euphococcine.

O-Unprotected keto- and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly substituted N-α-secondary and tertiary homoallylic hydroxylamines. The method was used in the total synthesis of the trace alkaloid N-Me-Euphococcine.

Synthesis of Highly Substituted Cyclopropanes via the Quasi-Favorskii Rearrangement of α,α-Dichlorocyclobutanols.

A method for the synthesis of highly substituted cyclopropanes via a quasi-Favorskii rearrangement is described. The method includes the combination two chemical transformations starting from α,α-dichlorocyclobutanones prepared via the [2 + 2] Staudinger ketene cycloaddition between either terminal- or cis-olefins and dichloroketene. First, α,α-dichlorocyclobutanones are reacted with organocerium reagents to afford the corresponding tertiary alcohols in good to excellent yields through a nucleophilic addition reaction that provided exclusively anti-products. Second, upon irreversible deprotonation, the tertiary α,α-dichlorocyclobutanols underwent a ring-contraction reaction (i.e., quasi-Favorskii rearrangement) to form structurally diverse cyclopropanes in moderate to good yields. The syn-stereoselectivity during the quasi-Favorskii rearrangement was evaluated using DFT analysis.

Occupancy versus colonization-extinction models for projecting population trends at different spatial scales.

Understanding spatiotemporal population trends and their drivers is a key aim in population ecology. We further need to be able to predict how the dynamics and sizes of populations are affected in the long term by changing landscapes and climate. However, predictions of future population trends are sensitive to a range of modeling assumptions. Deadwood-dependent fungi are an excellent system for testing the performance of different predictive models of sessile species as these species have different rarity and spatial population dynamics, the populations are structured at different spatial scales, and they utilize distinct substrates. We tested how the projected large-scale occupancies of species with differing landscape-scale occupancies are affected over the coming century by different modeling assumptions. We compared projections based on occupancy models against colonization-extinction models, conducting the modeling at alternative spatial scales and using fine- or coarse-resolution deadwood data. We also tested effects of key explanatory variables on species occurrence and colonization-extinction dynamics. The hierarchical Bayesian models applied were fitted to an extensive repeated survey of deadwood and fungi at 174 patches. We projected higher occurrence probabilities and more positive trends using the occupancy models compared to the colonization-extinction models, with greater difference for the species with lower occupancy, colonization rate, and colonization:extinction ratio than for the species with higher estimates of these statistics. The magnitude of future increase in occupancy depended strongly on the spatial modeling scale and resource resolution. We encourage using colonization-extinction models over occupancy models, modeling the process at the finest resource-unit resolution that is utilizable by the species, and conducting projections for the same spatial scale and resource resolution at which the model fitting is conducted. Further, the models applied should include key variables driving the metapopulation dynamics, such as the availability of suitable resource units, habitat quality, and spatial connectivity.

Enantioselective Catalytic Allylation of Acyclic Ketiminoesters: Synthesis of α-Fully-Substituted Amino Esters.

We report the first direct catalytic enantioselective allylation of acyclic α-ketiminoesters to afford α-allyl-α-aryl and α-allyl-α-trifluoromethyl amino esters in excellent isolated yield (91-99%) and with high optical purity (90-99+% ee). The allylation proceeds on a gram scale with 5-10 mol % of indium(I) iodide and commercially available BOX-type ligands. The allylated products are easily converted to enantiomerically enriched α-substituted proline derivatives.

Evaluating citizen science data for forecasting species responses to national forest management.

The extensive spatial and temporal coverage of many citizen science datasets (CSD) makes them appealing for use in species distribution modeling and forecasting. However, a frequent limitation is the inability to validate results. Here, we aim to assess the reliability of CSD for forecasting species occurrence in response to national forest management projections (representing 160,366 km2) by comparison against forecasts from a model based on systematically collected colonization-extinction data. We fitted species distribution models using citizen science observations of an old-forest indicator fungus Phellinus ferrugineofuscus. We applied five modeling approaches (generalized linear model, Poisson process model, Bayesian occupancy model, and two MaxEnt models). Models were used to forecast changes in occurrence in response to national forest management for 2020-2110. Forecasts of species occurrence from models based on CSD were congruent with forecasts made using the colonization-extinction model based on systematically collected data, although different modeling methods indicated different levels of change. All models projected increased occurrence in set-aside forest from 2020 to 2110: the projected increase varied between 125% and 195% among models based on CSD, in comparison with an increase of 129% according to the colonization-extinction model. All but one model based on CSD projected a decline in production forest, which varied between 11% and 49%, compared to a decline of 41% using the colonization-extinction model. All models thus highlighted the importance of protected old forest for P. ferrugineofuscus persistence. We conclude that models based on CSD can reproduce forecasts from models based on systematically collected colonization-extinction data and so lead to the same forest management conclusions. Our results show that the use of a suite of models allows CSD to be reliably applied to land management and conservation decision making, demonstrating that widely available CSD can be a valuable forecasting resource.

Predicting the decomposition of Scots pine, Norway spruce, and birch stems in Finland.

Models were developed for predicting the decomposition of dead wood for the main tree species in Finland, based on data collected from long-term thinning experiments in southern and central Finland. The decomposition rates were strongly related to the number of years after tree death. In contrast to previous studies, which have used the first-order exponential model, we found that the decomposition rate was not constant. Therefore, the Gompertz and Chapman-Richard's functions were fitted to the data. The slow initial decomposition period was mainly due to the fact that most dead trees remained standing as snags after their death. The initial period was followed by a period of rapid decomposition and, finally, by a period of moderately slow decomposition. Birch stems decomposed more rapidly than Scots pine and Norway spruce stems. Decomposition rates of Norway spruce stems were somewhat lower than those of Scots pine. Because the carbon concentration of decaying boles was relatively stable (about 50%) the rate of carbon loss follows that of mass loss. Models were also developed for the probability that a dead tree remains standing as a snag. During the first years after death, the probability was high. Thereafter, it decreased rapidly, the decrease being faster for birch stems than for Scots pine and Norway spruce stems. Almost all stems had fallen down within 40 years after their death. In Scots pine and Norway spruce, most snags remained hard and belonged to decay class 1. In birch, a higher proportion of snags belonged to the more advanced decay classes. The models provide a framework for predicting dead wood dynamics in managed as well as dense unthinned stands. The models can be incorporated into forest management planning systems, thereby facilitating estimates of carbon dynamics.