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

Partial tetraplegic syndrome as a complication of a mobilizing/manipulating procedure of the cervical spine in a man with Forestier's disease: a case report

<p>Abstract</p> <p>Introduction</p> <p>Even if performed by qualified physical therapists, spinal manipulation and mobilization can cause adverse events. This holds true particularly for the cervical spine. In light of the substantial risks, the benefits of cervical spine manipulation may be outweighed by the possibility of further injury.</p> <p>Case presentation</p> <p>We present the case of a 56-year-old Caucasian man with Forestier's disease who went to see a physiotherapist to relieve his aching neck while on a holiday trip. Following the procedure, he was transferred to a local hospital with a partial tetraplegic syndrome due to a cervical 6/7 luxation fracture. Reportedly, the physiotherapist took neither a detailed history, nor adequate diagnostic measures.</p> <p>Conclusions</p> <p>This case highlights the potentially dangerous complications associated with cervical spine mobilization/manipulation. If guidelines concerning cervical spine mobilization and manipulation practices had been followed, this adverse event could have been avoided.</p

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

Expedition 350 summary

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, and 1.5 km west of Ocean Drilling Program (ODP) Site 792, 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 a distinctive black glassy mafic ash layer that may record a large-volume subaqueous eruption 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 layer and its enclosing sediments and to better constrain its thickness. 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” because numerous ODP/Integrated Ocean Drilling Program sites had been drilled in the arc-front to fore-arc region (i.e., ODP Site 782A Leg 126), but this was the first site to be drilled in the rear-arc region 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 volcaniclastics 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 volcaniclastics 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 ~1300 mbsf 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 of solids is that arc-front versus rear-arc sources can be distinguished for individual intervals in the upper, relatively distal 1320 m of the section (Units I–V), whereas data for the lower, proximal 25% of the section (Units VI–VII) overlap and exceed the compositional fields for Neogene rear-arc seamounts and Quaternary arc-front volcanoes. This suggests that the compositional divergence between arc-front and rear-arc magmas only fully developed after ~13 Ma

Expedition 350 methods

Introduction This chapter of the International Ocean Discovery Program (IODP) Expedition 350 Proceedings volume documents the procedures and tools employed in the various shipboard laboratories of the R/V JOIDES Resolution during Expedition 350. This information applies only to shipboard work described in the Expedition Reports section of this volume. Methods for shore-based analyses of Expedition 350 samples and data will be described in the individual scientific contributions to be published in the open literature or in the Expedition Research Results section of this volume. This section describes procedures and equipment used for drilling, coring, and hole completion; core handling; computation of depth for samples and measurements; and sequence of shipboard analyses. Subsequent sections describe specific laboratory procedures and instruments in more details

Expedition 350 Methods

This chapter of the International Ocean Discovery Program (IODP) Expedition 350 Proceedings volume documents the procedures and tools employed in the various shipboard laboratories of the R/V JOIDES Resolution during Expedition 350. This information applies only to shipboard work described in the Expedition Reports section of this volume. Methods for shore-based analyses of Expedition 350 samples and data will be described in the individual scientific contributions to be published in the open literature or in the Expedition Research Results section of this volume. This section describes procedures and equipment used for drilling, coring, and hole completion; core handling; computation of depth for samples and measurements; and sequence of shipboard analyses. Subsequent sections describe specific laboratory procedures and instruments in more details