Palladium-catalyzed aerobic oxidative coupling of o-Xylene in flow:A Safe and Scalable Protocol for Cross-Dehydrogenative Coupling

\u3cp\u3eHerein, the first continuous cross-dehydrogenative homocoupling of an unactivated arene using oxygen as sole oxidant is reported. Employing microreactor technology which enables the use of elevated temperatures and pressures leads to a boost of the catalytic reaction. Hence, a major reduction in reaction time is achieved. Due to the significance as precursor for MOFs as well as high-tech and high-value polymers, the study focused on the production of 3,4,3′,4′-tetramethyl-biphenyl.\u3c/p\u3

Mild and selective base-free C–H arylation of heteroarenes:experiment and computation

A mild and selective C–H arylation strategy for indoles, benzofurans and benzothiophenes is described. The arylation method engages aryldiazonium salts as arylating reagents in equimolar amounts. The protocol is operationally simple, base free, moisture tolerant and air tolerant. It utilizes low palladium loadings (0.5 to 2.0 mol% Pd), short reaction times, green solvents (EtOAc/2-MeTHF or MeOH) and is carried out at room temperature, providing a broad substrate scope (47 examples) and excellent selectivity (C-2 arylation for indoles and benzofurans, C-3 arylation for benzothiophenes). Mechanistic experiments and DFT calculations support a Heck–Matsuda type coupling mechanism

Batch and flow synthesis of disulfides by visible-light-induced TiO2 photocatalysis

A mild and practical method for the preparation of disulfides through visible-light-induced photocatalytic aerobic oxidation of thiols has been developed. The method involves the use of TiO2 as a heterogeneous photocatalyst. The catalyst's high stability and recyclability makes this method highly practical. The reaction can be substantially accelerated in a continuous-flow packed-bed reactor, which enables a safe and reliable scale-up of the reaction conditions. The batch and flow protocol described herein can be applied to a diverse set of thiol substrates for the preparation of homo- and hetero-dimerized disulfides. Furthermore, biocompatible reaction conditions (i.e., room temperature, visible light, neutral buffer solution, and no additional base) have been developed, which permits the rapid and chemoselective modification of densely functionalized peptide substrates without recourse to complex purification steps.\u3cbr/\u3

Lower crustal hydrothermal circulation at slow-spreading ridges: evidence from chlorine in Arctic and South Atlantic basalt glasses and melt inclusions

Hydrothermal circulation at slow-spreading ridges is important for cooling the newly formed lithosphere, but the depth to which it occurs is uncertain. Magmas which stagnate and partially crystallize during their rise from the mantle provide a means to constrain the depth of circulation because assimilation of hydrothermal fluids or hydrothermally altered country rock will raise their chlorine (Cl) contents. Here we present Cl concentrations in combination with chemical thermobarometry data on glassy basaltic rocks and melt inclusions from the Southern Mid-Atlantic Ridge (SMAR; ~ 3 cm year−1 full spreading rate) and the Gakkel Ridge (max. 1.5 cm year−1 full spreading rate) in order to define the depth and extent of chlorine contamination. Basaltic glasses show Cl-contents ranging from ca. 50–430 ppm and ca. 40–700 ppm for the SMAR and Gakkel Ridge, respectively, whereas SMAR melt inclusions contain between 20 and 460 ppm Cl. Compared to elements of similar mantle incompatibility (e.g. K, Nb), Cl-excess (Cl/Nb or Cl/K higher than normal mantle values) of up to 250 ppm in glasses and melt inclusions are found in 75% of the samples from both ridges. Cl-excess is interpreted to indicate assimilation of hydrothermal brines (as opposed to bulk altered rock or seawater) based on the large range of Cl/K ratios in samples showing a limited spread in H2O contents. Resorption and disequilibrium textures of olivine, plagioclase and clinopyroxene phenocrysts and an abundance of xenocrysts and gabbroic fragments in the SMAR lavas suggest multiple generations of crystallization and assimilation of hydrothermally altered rocks that contain these brines. Calculated pressures of last equilibration based on the major element compositions of melts cannot provide reliable estimates of the depths at which this crystallization/assimilation occurred as the assimilation negates the assumption of crystallization under equilibrium conditions implicit in such calculations. Clinopyroxene–melt thermobarometry on rare clinopyroxene phenocrysts present in the SMAR magmas yield lower crustal crystallization/assimilation depths (10–13 km in the segment containing clinopyroxene). The Cl-excesses in SMAR melt inclusions indicate that assimilation occurred before crystallization, while also homogeneous Cl in melts from Gakkel Ridge indicate Cl addition during magma chamber processes. Combined, these observations imply that hydrothermal circulation reaches the lower crust at slow-spreading ridges, and thereby promotes cooling of the lower crust. The generally lower Cl-excess at slow-spreading ridges (compared to fast-spreading ridges) is probably related to them having few if any permanent magma chambers. Magmas therefore do not fractionate as extensively in the crust, providing less heat for assimilation (on average, slow-spreading ridge magmas have higher Mg#), and hydrothermal systems are ephemeral, leading to lower total degrees of crustal alteration and more variation in the amount of Cl contamination. Hydrothermal plumes and vent fields have samples in close vicinity that display Cl-excess, mostly of > 25 ppm, which thus can aid as a guide for the exploration of (active or extinct) hydrothermal vent fields on the axis