Preparation of amino-substituted indenes and 1,4-dihydronaphthalenes using a one-pot multireaction approach: total synthesis of oxybenzo[c]phenanthridine alkaloids

Allylic trichloroacetimidates bearing a 2-vinyl or 2-allylaryl group have been designed as substrates for a one-pot, two-step multi-bond-forming process leading to the general preparation of aminoindenes and amino-substituted 1,4-dihydronaphthalenes. The synthetic utility of the privileged structures formed from this one-pot process was demonstrated with the total synthesis of four oxybenzo[c]phenanthridine alkaloids, oxychelerythrine, oxysanguinarine, oxynitidine, and oxyavicine. An intramolecular biaryl Heck coupling reaction, catalyzed using the Hermann–Beller palladacycle was used to effect the key step during the synthesis of the natural products

Izu-Bonin-Mariana Rear Arc - The missing half of the subduction factory, 30 March – 30 May 2014

International Ocean Discovery Program (IODP) Hole U1436A (proposed Site IBM-4GT) lies in the western part of the Izu fore-arc basin, ~60 km east of the arc-front volcano Aogashima, ~170 km west of the axis of the Izu-Bonin Trench, 1.5 km west of Ocean Drilling Program (ODP) Site 792, and at 1776 meters below sea level (mbsl). It was drilled as a 150 m deep geotechnical test hole for potential future deep drilling (5500 meters below seafloor [mbsf]) at proposed Site IBM-4 using the D/V Chikyu. Core from Site U1436 yielded a rich record of Late Pleistocene explosive volcanism, including distinctive black glassy mafic ash layers that may record large-volume eruptions on the Izu arc front. Because of the importance of this discovery, Site U1436 was drilled in three additional holes (U1436B, U1436C, and U1436D), as part of a contingency operation, in an attempt to get better recovery on the black glassy mafic ash layers and enclosing sediments and to better constrain the thickness of the mafic ash layers. IODP Site U1437 is located in the Izu rear arc, ~330 km west of the axis of the Izu-Bonin Trench and ~90 km west of the arc-front volcanoes Myojinsho and Myojin Knoll, at 2117 mbsl. The primary scientific objective for Site U1437 was to characterize “the missing half of the subduction factory”; this was because numerous ODP/Integrated Ocean Drilling Program sites had been drilled in the arc to fore-arc region (i.e., ODP Site 782A Leg 126), but this was the first site to be drilled in the rear part of the Izu arc. A complete view of the arc system is needed to understand the formation of oceanic arc crust and its evolution into continental crust. Site U1437 on the rear arc had excellent core recovery in Holes U1437B and U1437D, and we succeeded in hanging the longest casing ever in the history of R/V JOIDES Resolution scientific drilling (1085.6 m) in Hole U1437E and cored to 1806.5 mbsf. The stratigraphy at Site U1437 was divided into seven lithostratigraphic units (I–VII) that were distinguished from each other based on the proportions and characteristics of tuffaceous mud/mudstone and interbedded tuff, lapilli tuff, and tuff breccia. The section is much more mud rich than expected, with ~60% tuffaceous mud for the section as a whole (89% in the uppermost 433 m) and high sedimentation rates of 100–260 m/My for the upper 1320 m (Units I–V). The proportion (40%) and grain size of tephra are much smaller than expected for an intra-arc basin, composed half of ash/tuff and half of lapilli tuff of fine grain size (clasts < 3 cm). These were deposited by suspension settling through water and from density currents, in relatively distal settings. Volcanic blocks are only sparsely scattered through the lowermost 25% of the section (Units VI and VII, 1320–1806.5 mbsf), which includes hyaloclastite, in situ quench-fragmented blocks, and a rhyolite peperite intrusion (i.e., proximal deposits). The transition from unconsolidated to lithified rocks occurred progressively; however, sediments were considered lithified from 427 mbsf (top of Hole U1437D) downward. Alteration resulted in destruction of fresh glass from ~750 mbsf downward, but minerals are less altered. Because of the alteration, the deepest biostratigraphic datum was at ~850 mbsf and the deepest paleomagnetic datum was at ~1300 mbsf. Additional age control deeper than this depth is provided by an age range of 10.97–11.85 Ma inferred from a nannofossil assemblage at ~1403 mbsf and a preliminary U-Pb zircon concordia intercept age of 13.6 +1.6/–1.7 Ma, measured postcruise on a rhyolite peperite in Unit VI at ~1390 mbsf. Based on the seismic profiles, the Miocene–Oligocene hiatus (~17–23 Ma) was predicted to lie at ~1250 mbsf, but strata at that depth (Unit V, 1120–1312 mbsf) are much younger (~9 Ma), indicating that we recovered a thicker Neogene section of volcaniclastics and associated igneous rocks than anticipated. Our preliminary interpretation of shipboard geochemistry is that arc-front versus rear-arc sources can be distinguished in the upper, relatively distal 1320 m of section (Units I–V), whereas the lower, proximal 25% of the section (Units VI–VII) may be geochemically heterogeneous, suggesting that the rear-arc magmas only fully compositionally diverged after ~13 Ma

International Ocean Discovery Program Expedition 350 Preliminary Report Izu-Bonin-Mariana Rear Arc The missing half of the subduction factory

International Ocean Discovery Program (IODP) Hole U1436A (proposed Site IBM-4GT) lies in the western part of the Izu fore-arc basin, ~60 km east of the arc-front volcano Aogashima, ~170 km west of the axis of the Izu-Bonin Trench, 1.5 km west of Ocean Drilling Program (ODP) Site 792, and at 1776 meters below sea level (mbsl). It was drilled as a 150 m deep geotechnical test hole for potential future deep drilling (5500 meters below seafloor [mbsf]) at proposed Site IBM-4 using the D/V Chikyu. Core from Site U1436 yielded a rich record of Late Pleistocene explosive volcanism, including distinctive black glassy mafic ash layers that may record large-volume eruptions on the Izu arc front. Because of the importance of this discovery, Site U1436 was drilled in three additional holes (U1436B, U1436C, and U1436D), as part of a contingency operation, in an attempt to get better recovery on the black glassy mafic ash layers and enclosing sediments and to better constrain the thickness of the mafic ash layers. IODP Site U1437 is located in the Izu rear arc, ~330 km west of the axis of the Izu-Bonin Trench and ~90 km west of the arc-front volcanoes Myojinsho and Myojin Knoll, at 2117 mbsl. The primary scientific objective for Site U1437 was to characterize “the missing half of the subduction factory”; this was because numerous ODP/Integrated Ocean Drilling Program sites had been drilled in the arc to fore-arc region (i.e., ODP Site 782A Leg 126), but this was the first site to be drilled in the rear part of the Izu arc. A complete view of the arc system is needed to understand the formation of oceanic arc crust and its evolution into continental crust. Site U1437 on the rear arc had excellent core recovery in Holes U1437B and U1437D, and we succeeded in hanging the longest casing ever in the history of R/V JOIDES Resolution scientific drilling (1085.6 m) in Hole U1437E and cored to 1806.5 mbsf. The stratigraphy at Site U1437 was divided into seven lithostratigraphic units (I–VII) that were distinguished from each other based on the proportions and characteristics of tuffaceous mud/mudstone and interbedded tuff, lapilli tuff, and tuff breccia. The section is much more mud rich than expected, with ~60% tuffaceous mud for the section as a whole (89% in the uppermost 433 m) and high sedimentation rates of 100–260 m/My for the upper 1320 m (Units I–V). The proportion (40%) and grain size of tephra are much smaller than expected for an intra-arc basin, composed half of ash/tuff and half of lapilli tuff of fine grain size (clasts < 3 cm). These were deposited by suspension settling through water and from density currents, in relatively distal settings. Volcanic blocks are only sparsely scattered through the lowermost 25% of the section (Units VI and VII, 1320–1806.5 mbsf), which includes hyaloclastite, in situ quench-fragmented blocks, and a rhyolite peperite intrusion (i.e., proximal deposits). The transition from unconsolidated to lithified rocks occurred progressively; however, sediments were considered lithified from 427 mbsf (top of Hole U1437D) downward. Alteration resulted in destruction of fresh glass from ~750 mbsf downward, but minerals are less altered. Because of the alteration, the deepest biostratigraphic datum was at ~850 mbsf and the deepest paleomagnetic datum was at ~1300 mbsf. Additional age control deeper than this depth is provided by an age range of 10.97–11.85 Ma inferred from a nannofossil assemblage at ~1403 mbsf and a preliminary U-Pb zircon concordia intercept age of 13.6 +1.6/–1.7 Ma, measured postcruise on a rhyolite peperite in Unit VI at ~1390 mbsf. Based on the seismic profiles, the Miocene–Oligocene hiatus (~17–23 Ma) was predicted to lie at ~1250 mbsf, but strata at that depth (Unit V, 1120–1312 mbsf) are much younger (~9 Ma), indicating that we recovered a thicker Neogene section of volcaniclastics and associated igneous rocks than anticipated. Our preliminary interpretation of shipboard geochemistry is that arc-front versus rear-arc sources can be distinguished in the upper, relatively distal 1320 m of section (Units I–V), whereas the lower, proximal 25% of the section (Units VI–VII) may be geochemically heterogeneous, suggesting that the rear-arc magmas only fully compositionally diverged after ~13 Ma

Contribution of mesothelial cells in the expression of inflammatory-related factors in omental adipose tissue of obese subjects.

OBJECTIVE: The objective of this study was to determine the contribution of mesothelial cells, present in human omental adipose tissue (OAT) but not in the subcutaneous depot (SAT), on the expression of inflammation-related factors. DESIGN: Comparison of the expression profiles of inflammation-related genes in mesothelial cells with those in the adipocyte-enriched (AEF) and stromal vascular fractions (SVF) and localization of interleukin-18 (IL-18) expression in adipose depots. SUBJECTS: Eleven obese Caucasian female subjects undergoing gastric bypass surgery (body mass index: 43.6+/-1.3 kg/m(2); age: 41.6+/-2.3 years). MEASUREMENTS: The expression profiles of cytokine and chemokine-related genes in mesothelial cells and in cell fractions prepared from OAT were assessed by the microarray technique. The differential expression of IL-18 was confirmed by real-time PCR and the protein was localized in adipose depots by immunohistochemistry. RESULTS: Microarray data analysis demonstrated that, of the 16 cytokine and chemokine-related genes that were upregulated in mesothelial cells compared with the AEF, IL-18 was the cytokine with the highest differential expression. IL-18 expression was similar in mesothelial cells and the SVF. In both SAT and OAT, IL-18 was immunolocalized in neutrophils and mast cells, but not in macrophages nor adipocytes. This cytokine was also detected in mesothelial cells in OAT. This additional source of expression may explain the higher IL-18 expression levels in OAT than SAT (+5.9-fold). CONCLUSION: By their capacity to express inflammatory-related factors, and in particular the proinflammatory cytokine IL-18 in OAT, mesothelial cells appear as a new player in the process of low-grade inflammation associated with obesity

Enantioselective Synthesis of Polycyclic Nitrogen Heterocycles by Rh-Catalyzed Alkene Hydroacylation: Constructing Six-Membered Rings in the Absence of Chelation Assistance

[Image: see text] Catalytic, enantioselective hydroacylations of N-allylindole-2-carboxaldehydes and N-allylpyrrole-2-carboxaldehydes are reported. In contrast to many alkene hydroacylations that form six-membered rings, these annulative processes occur in the absence of ancillary functionality to stabilize the acylrhodium(III) hydride intermediate. The intramolecular hydroacylation reactions generate 7,8-dihydropyrido[1,2-a]indol-9(6H)ones and 6,7-dihydroindolizin-8(5H)-ones in moderate to high yields with excellent enantioselectivities

Palladium complexes of the Heterodiphosphineo-C6H4(CH2PtBu2)(CH2PPh2) are highly selective and robust catalysts for the Hydromethoxycarbonylation of Ethene

The coordination chemistry and ethene hydromethoxycarbonylation catalysis with the diphosphine o-C6H4(CH2PtBu2)(CH2PPh2) (L3) is reported and the results compared with the analogous chemistry of the symmetrical diphosphines o-C6H4(CH2PtBu2)2 (L1) and o-C6H4(CH2PPh2)2 (L2). Palladium-catalyzed ethene hydromethoxycarbonylation studies under the commercial catalytic conditions are reported. The results obtained using L1−3 as supporting ligands show that the catalysts derived from L3 and L1 have similar activity and selectivity for methyl propanoate (MeP). In addition, the Pd−L3 catalyst has much greater longevity than the Pd−L1 catalyst. Treatment of the appropriate [Pt(X)(Y)(cod)] with L3 gave [PtCl2(L3)] (3), [Pt(CH3)2(L3)] (6), and [PtCl(CH3)(L3)] (9). At equilibrium, complex 9 is a 90:1 mixture of geometric isomers 9a (with CH3 trans to the tBu2P) and 9b (with Cl trans to the tBu2P). The fluxionality of complex 3, detected by 1H NMR, is interpreted in terms of the conformation of the seven-membered chelate. The complexes [Pt(CH3)(PMe3)(L3)]Cl (10b) and [PtH(PPh3)(L3)]Cl (12b) are formed as essentially single isomers with CH3/H trans to the Ph2P group. The palladium complexes [PdCl2(L3)] (13), [PdCl(CH3)(L3)] (14a/14b), and [PdH(PCy3)(L3)]BF4 (15b) have been made by similar methods to their platinum analogues. The factors controlling the relative isomer stabilities are explored experimentally and computationally. The complexes [PtCl2(L4)] (16) and [PtCl(CH3)(L4)] (17a/17b) where L4 = o-C6H4(CH2PnBu2)(CH2PPh2) are reported, and the geometric isomers of 17 are almost isoenergetic. The crystal structures of 3, 14a, 15b, and 16 have been determined by X-ray crystallography. DFT calculations on complexes of the type [Pt(X)(Y)(L3)] gave only small calculated differences in energy between the geometrical isomers (0−4 kcal mol−1), which are consistent with the experimental observations. It is suggested that repulsive intramolecular H···H interactions (between the Pt−CH3 and PC(CH3)3 groups) determine which isomer predominates. The reasons for the favorable catalytic properties of the Pd−L3 catalyst are probed by 13CO reactions with the model complexes 9a/9b and 14a/14b, and the structures of the resulting acyl complexes are assigned on the basis of 13C and 31P NMR and IR spectroscopy. From these studies, it is suggested that the reason for the Pd−L3 catalyst resembling the Pd−L1 catalyst in terms of selectivity is that the crucial acyl intermediates are similar

Martigny Bourg au XIXe siècle: inventaire des bâtiments et typologie architecturale

The asynchronous relationship between millennial-scale temperature changes over Greenland and Antarctica during the last glacial period has led to the notion of a bipolar seesaw which acts to redistribute heat depending on the state of meridional overturning circulation within the Atlantic Ocean. Here we present new records from the South Atlantic that show rapid changes during the last deglaciation that were instantaneous (within dating uncertainty) and of opposite sign to those observed in the North Atlantic. Our results demonstrate a direct link between the abrupt changes associated with variations in the Atlantic meridional overturning circulation and the more gradual adjustments characteristic of the Southern Ocean. These results emphasize the importance of the Southern Ocean for the development and transmission of millennial-scale climate variability and highlight its role in deglacial climate change and the associated rise in atmospheric carbon dioxide