Oxidative Coupling as a Biomimetic Approach to the Synthesis of Scytonemin

The first total synthesis of the dimeric alkaloid pigment scytonemin is described. The key transformations In Its synthesis from 3-indole acetic acid are a Heck carbocyclization and a Suzuki-Miyaura cross-coupling, orchestrated In a stereospecific tandem fashion, followed by a biosynthetically inspired oxidative dimerization. The tandem sequence generates a tetracyclic (E)-3-(arylidene)-3,4-dihydrocyclopenta[b]indol-2(1H)-one that is subsequently dimerized into the unique homodimeric core structure of scytonemin

Tectono-thermal evolution of Oman's Mesozoic passive continental margin under the obducting Semail Ophiolite: a case study of Jebel Akhdar, Oman

We present a study of pressure and temperature evolution in the passive continental margin under the Oman Ophiolite using numerical basin models calibrated with thermal maturity data, fluid-inclusion thermometry, and low-temperature thermochronometry and building on the results of recent work on the tectonic evolution. Because the Oman mountains experienced only weak post-obduction overprint, they offer a unique natural laboratory for this study. Thermal maturity data from the Adam Foothills constrain burial in the basin in front of the advancing nappes to at least 4&thinsp;km. Peak temperature evolution in the carbonate platform under the ophiolite depends on the burial depth and only weakly on the temperature of the overriding nappes, which have cooled during transport from the oceanic subduction zone to emplacement. Fluid-inclusion thermometry yields pressure-corrected homogenization temperatures of 225 to 266&thinsp;∘C for veins formed during progressive burial, 296–364&thinsp;∘C for veins related to peak burial, and 184 to 213&thinsp;∘C for veins associated with late-stage strike-slip faulting. In contrast, the overlying Hawasina nappes have not been heated above 130–170&thinsp;∘C, as witnessed by only partial resetting of the zircon (U-Th)/He thermochronometer. In combination with independently determined temperatures from solid bitumen reflectance, we infer that the fluid inclusions of peak-burial-related veins formed at minimum pressures of 225–285&thinsp;MPa. This implies that the rocks of the future Jebel Akhdar Dome were buried under 8–10&thinsp;km of ophiolite on top of 2&thinsp;km of sedimentary nappes, in agreement with thermal maturity data from solid bitumen reflectance and Raman spectroscopy. Rapid burial of the passive margin under the ophiolite results in sub-lithostatic pore pressures, as indicated by veins formed in dilatant fractures in the carbonates. We infer that overpressure is induced by rapid burial under the ophiolite. Tilting of the carbonate platform in combination with overpressure in the passive margin caused fluid migration towards the south in front of the advancing nappes. Exhumation of the Jebel Akhdar, as indicated by our zircon (U-Th)/He data and in agreement with existing work on the tectonic evolution, started as early as the Late Cretaceous to early Cenozoic, linked with extension above a major listric shear zone with top-to-NNE shear sense. In a second exhumation phase the carbonate platform and obducted nappes of the Jebel Akhdar Dome cooled together below ca. 170&thinsp;∘C between 50 and 40&thinsp;Ma before the final stage of anticline formation.</p

Bioavailability of Macro and Micronutrients Across Global Topsoils: Main Drivers and Global Change Impacts

Understanding the chemical composition of our planet\u27s crust was one of the biggest questions of the 20th century. More than 100 years later, we are still far from understanding the global patterns in the bioavailability and spatial coupling of elements in topsoils worldwide, despite their importance for the productivity and functioning of terrestrial ecosystems. Here, we measured the bioavailability and coupling of thirteen macro- and micronutrients and phytotoxic elements in topsoils (3–8 cm) from a range of terrestrial ecosystems across all continents (∼10,000 observations) and in response to global change manipulations (∼5,000 observations). For this, we incubated between 1 and 4 pairs of anionic and cationic exchange membranes per site for a mean period of 53 days. The most bioavailable elements (Ca, Mg, and K) were also amongst the most abundant in the crust. Patterns of bioavailability were biome-dependent and controlled by soil properties such as pH, organic matter content and texture, plant cover, and climate. However, global change simulations resulted in important alterations in the bioavailability of elements. Elements were highly coupled, and coupling was predictable by the atomic properties of elements, particularly mass, mass to charge ratio, and second ionization energy. Deviations from the predictable coupling-atomic mass relationship were attributed to global change and agriculture. Our work illustrates the tight links between the bioavailability and coupling of topsoil elements and environmental context, human activities, and atomic properties of elements, thus deeply enhancing our integrated understanding of the biogeochemical connections that underlie the productivity and functioning of terrestrial ecosystems in a changing world

Novel class of tertiary phosphine ligands based on a phospha-adamantane framework and use in the Suzuki cross-coupling reactions of aryl halides under mild conditions

A new class of sterically hindered phosphines based on a phospha-adamantane framework is described. Arylation or alkylation of the 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane system allows for the preparation of tertiary phosphines suitable for use in palladium-catalyzed cross-coupling reactions. For example, use of a catalytic system incorporating Pd2(dba)3 and 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phospha-adamantane is shown to promote the Suzuki cross-coupling of aryl iodides, bromides, and activated chlorides with a variety of aryl boronic acids at room temperature in a few hours with high yields