Pd-catalyzed enantioselective aerobic oxidation of secondary alcohols: Applications to the total synthesis of alkaloids

Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described

A Convergent and Enantioselective Synthesis of (+)-Amurensinine via Selective C−H and C−C Bond Insertion Reactions

A convergent and enantioselective synthesis of the natural product amurensinine is described. The synthetic strategy takes advantage of mild and selective C−H and C−C bond insertion reactions, in addition to the palladium-catalyzed aerobic oxidative kinetic resolution recently developed in these laboratories

Inter-decadal variation in diadromous and potamodromous fish assemblages in a near pristine tropical dryland river

Freshwater ecosystems are both incredibly biodiverse and highly threatened globally. Variation in environmental parameters including habitat and flow can substantially affect many ecological processes within riverine aquatic communities, but the ties between such parameters and ecology are neither well studied nor understood. In highly variable tropical dryland river systems, assessing such relationships requires data collection over inter-decadal time scales, which is not typically permitted on development schedules driven over short periods (including election and funding cycles). Here, we used seine net sampling data collected over an 18-year period in the tropical dryland Fitzroy River, Western Australia, to assess how environmental and temporal factors including habitat, seasonality, and inter-annual variation in wet season magnitude affect the community assemblage structure, recruitment, and growth of aquatic species in dryland rivers. Results demonstrated that macrohabitat (main channel vs floodplain creek) and the magnitude of wet season rains and resultant flooding both had a substantial influence on biotic communities, alongside seasonal and diel variation. The magnitude of wet season flooding (measured as river discharge volume) had the greatest impact on assemblage composition within floodplain creek habitats and was a significant driver of recruitment rates and growth of recruits and adults of several species examined. This study highlights key considerations for conserving dryland river systems and constituent biota. Specifically, these are maintaining (a) rhythmicity of flow within each year, (b) diversity of flow volume between years, and (c) a variety of habitat types including ephemeral, semi-permanent, and permanent shallow floodplain and deeper main channel pools, in order to support a diverse array of generalist and specialist diadromous and potamodromous fishes

Oxytocin alters patterns of brain activity and amygdalar connectivity by age during dynamic facial emotion identification

Aging is associated with increased difficulty in facial emotion identification, possibly due to age-related network change. The neuropeptide oxytocin (OT) facilitates emotion identification, but this is understudied in aging. To determine the effects of OT on dynamic facial emotion identification across adulthood, 46 young and 48 older participants self-administered intranasal OT or a placebo in a randomized, double-blind procedure. Older participants were slower and less accurate in identifying emotions. Although there was no behavioral treatment effect, partial least squares analysis supported treatment effects on brain patterns during emotion identification that varied by age and emotion. For young participants, OT altered the processing of sadness and happiness, whereas for older participants, OT only affected the processing of sadness (15.3% covariance, p\ua0= 0.004). Furthermore, seed partial least squares analysis showed that older participants in the OT group recruited a large-scale amygdalar network that was positively correlated for anger, fear, and happiness, whereas older participants in the placebo group recruited a smaller, negatively correlated network (7% covariance, p\ua0= 0.002). Advancing the literature, these findings show that OT alters brain activity and amygdalar connectivity by age and emotion

Catalytic enantioselective stereoablative reactions: an unexploited approach to enantioselective catalysis

Approaches to the preparation of enantioenriched materials via catalytic methods that destroy stereogenic elements of a molecule are discussed. Although these processes often decrease overall molecular complexity, there are several notable advantages including material recycling, enantiodivergence and convergence, and increased substrate scope. Examples are accompanied by discussion of the critical design elements required for the success of these methods

The direct acyl-alkylation of arynes. Preparation of methyl 2-(2-acetylphenyl)acetate

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A Convergent and Enantioselective Synthesis of (+)-Amurensinine via Selective C−H and C−C Bond Insertion Reactions

A convergent and enantioselective synthesis of the natural product amurensinine is described. The synthetic strategy takes advantage of mild and selective C−H and C−C bond insertion reactions, in addition to the palladium-catalyzed aerobic oxidative kinetic resolution recently developed in these laboratories

Amphidromy Links a Newly Documented Fish Community of Continental Australian Streams, to Oceanic Islands of the West Pacific

BACKGROUND: Indo-Pacific high island streams experience extreme hydrological variation, and are characterised by freshwater fish species with an amphidromous life history. Amphidromy is a likely adaptation for colonisation of island streams following stochastic events that lead to local extirpation. In the Wet Tropics of north-eastern Australia, steep coastal mountain streams share similar physical characteristics to island systems. These streams are poorly surveyed, but may provide suitable habitat for amphidromous species. However, due to their ephemeral nature, common non-diadromous freshwater species of continental Australia are unlikely to persist. Consequently, we hypothesise that coastal Wet Tropics streams are faunally more similar, to distant Pacific island communities, than to nearby faunas of large continental rivers. METHODS/PRINCIPAL FINDINGS: Surveys of coastal Wet Tropics streams recorded 26 species, 10 of which are first records for Australia, with three species undescribed. This fish community is unique in an Australian context in that it contains mostly amphidromous species, including sicydiine gobies of the genera Sicyopterus, Sicyopus, Smilosicyopus and Stiphodon. Species presence/absence data of coastal Wet Tropics streams were compared to both Wet Tropics river networks and Pacific island faunas. ANOSIM indicated the fish fauna of north-eastern Australian coastal streams were more similar to distant Pacific islands (R = 0.76), than to nearby continental rivers (R = 0.98). MAIN CONCLUSIONS/SIGNIFICANCE: Coastal Wet Tropics streams are faunally more similar to distant Pacific islands (79% of species shared), than to nearby continental fauna due to two factors. First, coastal Wet Tropics streams lack many non-diadromous freshwater fish which are common in nearby large rivers. Second, many amphidromous species found in coastal Wet Tropics streams and Indo-Pacific islands remain absent from large rivers of the Wet Tropics. The evolutionary and conservation significance of this newly discovered Australian fauna requires clarification in the context of the wider amphidromous fish community of the Pacific