Catalytic enantioselective synthesis of carbocyclic and heterocyclic spiranes via a decarboxylative aldol cyclization

The synthesis of a variety of enantioenriched 1,3-diketospiranes from the corresponding racemic allyl β-ketoesters via an interrupted asymmetric allylic alkylation is disclosed. Substrates possessing pendant aldehydes undergo decarboxylative enolate formation in the presence of a chiral Pd catalyst and subsequently participate in an enantio- and diastereoselective, intramolecular aldol reaction to furnish spirocyclic β-hydroxy ketones which may be oxidized to the corresponding enantioenriched diketospiranes. Additionally, this chemistry has been extended to α-allylcarboxy lactam substrates leading to a formal synthesis of the natural product (−)-isonitramine

Catalytic enantioselective synthesis of carbocyclic and heterocyclic spiranes via a decarboxylative aldol cyclization

The synthesis of a variety of enantioenriched 1,3-diketospiranes from the corresponding racemic allyl β-ketoesters via an interrupted asymmetric allylic alkylation is disclosed. Substrates possessing pendant aldehydes undergo decarboxylative enolate formation in the presence of a chiral Pd catalyst and subsequently participate in an enantio- and diastereoselective, intramolecular aldol reaction to furnish spirocyclic β-hydroxy ketones which may be oxidized to the corresponding enantioenriched diketospiranes. Additionally, this chemistry has been extended to α-allylcarboxy lactam substrates leading to a formal synthesis of the natural product (−)-isonitramine

Agglutination of benthic foraminifera in relation to mesoscale bathymetric features in the abyssal NE Atlantic (Porcupine Abyssal Plain)

Abyssal hills, small topographic features rising above the abyssal seafloor (< 1000 m altitude), have distinct environmental characteristics compared to abyssal plains, notably the presence of coarser-grained sediments. As a result, they are a major source of habitat heterogeneity in the deep sea. The aim of this study was to investigate whether there is a link between abyssal hills and the test characteristics of selected agglutinated benthic foraminiferal species. We analysed 1) the overall morphometry, and 2) the granulometric and chemical (elemental) characteristics of the agglutinated tests of ten common foraminiferal species (Adercotryma glomerata, Ammobaculites agglutinans, Cribrostomoides subglobosus, Lagenammina sp.1, Nodulina dentaliniformis, Portatrochammina murrayi, three Reophax sp. and Recurvoides sp. 9) at four sites (two on top of abyssal hills and two on the adjacent plain) in the area of the Porcupine Abyssal Plain Sustained Observatory, northeast Atlantic. The foraminiferal test data were compared with the particle size distribution and elemental composition of sediments from the study sites in order to explore possible grain size and mineral selectivity. We found differences in the visual appearance of the tests (i.e. the degree of irregularity in their shape), which was confirmed by morphometric analyses, related to seafloor topography. The agglutinated foraminifera selected different sized particles on hills and plains, reflecting the distinct granulometric characteristics of these settings. These characteristics (incorporation of coarse particles, test morphometry) could provide evidence for the recognition of ancient abyssal hill environments, as well as other palaeoceanographic settings that were characterised by enhanced current flow. Furthermore, analyses of sediment samples from the hill and plain sites using wavelength dispersive X-ray fluorescence (WD-XRF) yielded different elemental profiles from the plains, probably a result of winnowing on the hills, although all samples were carbonate-rich. In contrast, the majority of the agglutinated tests were rich in silica, suggesting a preferential selection for quartz

Ballasting by cryogenic gypsum enhances carbon export in a Phaeocystis under-ice bloom

Mineral ballasting enhances carbon export from the surface to the deep ocean; however, little is known about the role of this process in the ice-covered Arctic Ocean. Here, we propose gypsum ballasting as a new mechanism that likely facilitated enhanced vertical carbon export from an under-ice phytoplankton bloom dominated by the haptophyte Phaeocystis. In the spring 2015 abundant gypsum crystals embedded in Phaeocystis aggregates were collected throughout the water column and on the sea floor at a depth below 2 km. Model predictions supported by isotopic signatures indicate that 2.7 g m-2 gypsum crystals were formed in sea ice at temperatures below -6.5 °C and released into the water column during sea ice melting. Our finding indicates that sea ice derived (cryogenic) gypsum is stable enough to survive export to the deep ocean and serves as an effective ballast mineral. Our findings also suggest a potentially important and previously unknown role of Phaeocystis in deep carbon export due to cryogenic gypsum ballasting. The rapidly changing Arctic sea ice regime might favour this gypsum gravity chute with potential consequences for carbon export and food partitioning between pelagic and benthic ecosystems.Publisher PDFPeer reviewe