Late Silurian to early Devonian development of the Chingiz accretion arc, West Junggar: insights into accretion arc evolution in the Central Asia Orogenic Belt

Early Palaeozoic evolution of the Kazakhstan orocline in the Central Asian Orogenic Belt (CAOB) is key to reconstructing the Palaeozoic tectonic framework in Central Asia. This study presents field mapping, geochemistry, and geochronological data from the Wulasitai area of northern West Junggar to constrain the subduction polarity and major tectonic events in the Chingiz arc of the Kazakhstan orocline during the Early Palaeozoic. The mapping area outcrops imbricated coherent turbidite slices and mélanges that consist of chert, limestone, silt, sandstone, and conglomerate blocks in mudstone matrix, representing an OPS (Ocean Plate Stratigraphy) mélange in an accretionary complex. Existing fossil ages from these blocks range from the Ordovician to Silurian, while our new detrital zircon U-Pb samples from the turbiditic matrix yield maximum depositional ages (MDTs) from 428\ua0±\ua02\ua0Ma to 450\ua0±\ua01\ua0Ma. Detrital zircon ages of ~510 to 430\ua0Ma in the mélange suggest the Chingiz arc to the south of the study area as a major sediment source, providing an indirect constraint on the polarity of subduction. We suggest that the northern part of the Chingiz arc may be underlain by southward subduction, with the accretionary complex located on the Wulasitai area of the northern West Junggar. The Wulasitai mélange is overlain depostionally by volcanic rocks carrying depleted HFSE and enriched LILE, LREE. The andesite and tuff are dated to 415\ua0±\ua05\ua0Ma, 414\ua0±\ua03\ua0Ma, and 402\ua0±\ua06\ua0Ma, which we interpret as reflecting the development of the volcanic arc onto the previous subduction complex. This model implies the generation of the arc (accretion arc) as the slab rolling back and trench retreating, which may play an important role in the evolutionary history of CAOB

Copper-Mediated C–H Activation/C–S Cross-Coupling of Heterocycles with Thiols

We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C–H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na₂CO₃. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu­(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper–thiolate complex [(L)­Cu­(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis

Oxygen mediated oxidative couplings of flavones in alkaline water

Catalyzed oxidative C-C bond coupling reactions play an important role in the chemical synthesis of complex natural products of medicinal importance. However, the poor functional group tolerance renders them unfit for the synthesis of naturally occurring polyphenolic flavones. We find that molecular oxygen in alkaline water acts as a hydrogen atom acceptor and oxidant in catalyst-free (without added catalyst) oxidative coupling of luteolin and other flavones. By this facile method, we achieve the synthesis of a small collection of flavone dimers and trimers including naturally occurring dicranolomin, philonotisflavone, dehydrohegoflavone, distichumtriluteolin, and cyclodistichumtriluteolin. Mechanistic studies using both experimental and computational chemistry uncover the underlying reasons for optimal pH, oxygen availability, and counter-cations that define the success of the reaction. We expect our reaction opens up a green and sustainable way to synthesize flavonoid dimers and oligomers using the readily available monomeric flavonoids isolated from biomass and exploiting their use for health care products and treatment of diseases