An efficient and practical system for inexpensive bromination and iodination of arenes as well as heteroarenes by using readily available dimethyl sulfoxide (DMSO) and HX (X = Br, I) reagents is reported. This mild oxidative system demonstrates a versatile protocol for the synthesis of aryl halides. HX (X = Br, I) are employed as halogenating reagents when combined with DMSO which participates in the present chemistry as a mild and inexpensive oxidant. This oxidative system is amenable to late-stage bromination of natural products. The kilogram-scale experiment (>95% yield) shows great potential for industrial application.

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

The nucleotides diadenosine triphosphate (Ap3A) and diadenosine tetraphosphate (Ap4A) are formed in prokaryotic and eukaryotic cells. Since their concentrations increase significantly upon cellular stress, they are considered to be alarmones triggering stress adaptive processes. However, their cellular roles remain elusive. To elucidate the proteome-wide interactome of Ap3A and Ap4A and thereby gain insights into their cellular roles, we herein report the development of photoaffinity-labeling probes and their employment in chemical proteomics. We demonstrate that the identified ApnA interactors are involved in many fundamental cellular processes including carboxylic acid and nucleotide metabolism, gene expression, various regulatory processes and cellular response mechanisms and only around half of them are known nucleotide interactors. Our results highlight common functions of these ApnAs across the domains of life, but also identify those that are different for Ap3A or Ap4A. This study provides a rich source for further functional studies of these nucleotides and depicts useful tools for characterization of their regulatory mechanisms in cells.

Quasi-two-dimensional kagome metals AV3Sb5 (A = Cs, Rb, and Cs) have attracted much recent interest due to fascinating quantum phenomena such as giant anomalous Hall effect, topological charge order, and unconventional superconductivity. Here we report pressure-induced reemergent superconductivity in CsV3Sb5 by electrical transport measurements under high pressures up to 47.9 GPa. We show that the superconducting critical temperature Tc is first enhanced by pressure and reaches its first maximum ~ 8.9 K at 0.8 GPa, then the Tc is suppressed by pressure and cannot be detected above 7.5 GPa, forming a dome-shaped superconducting phase diagram. Remarkably, upon further compression above 16.5 GPa, a new superconducting state arises, of which Tc is enhanced by pressure to a second maximum ~ 5.0 K and the reemergent superconductivity keeps robust up to 47.9 GPa. Combined with synchrotron x-ray diffraction measurements that demonstrate the stability of the pristine hexagonal phase up to 43.1 GPa, we argue that the reemergence of superconductivity in the V-based superconductor could be attributed to a pressure-induced Lifshitz transition. Introduction--Recently, a class of quasi-two-dimensional topological Kagome metals AV3Sb5 (A= K, Rb, and Cs) has been attracting great interest. Combination of topologically nontrivial electronic structure and strong correlated effects lead to a series of fascinating quantum phenomena in these compounds, such as novel superconductivity [1-6], charge density wave (CDW) [4,5,[7][8][9][10][11][12][13], and giant anomalous Hall effect [14,15]. A robust zero-bias conductance peak inside the superconducting (SC) vortex core was observed in CsV3Sb5, implying topological superconductivity [8]. Scanning tunneling microscope/spectroscopy (STM/STS) revealed that the