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Acyl Suzuki cross-coupling involves the coupling of an organoboron reagent with an acyl electrophile (acyl halide, anhydride, ester, amide). This review provides a timely overview of the very important advances that have recently taken place in the acylative Suzuki cross-coupling. Particular emphasis is directed toward the type of acyl electrophiles, catalyst systems and new cross-coupling partners. This review will be of value to synthetic chemists involved in this rapidly developing field of Suzuki cross-coupling as well as those interested in using acylative Suzuki cross-coupling for the synthesis of ketones as a catalytic alternative to stoichiometric nucleophilic additions or Friedel-Crafts reactions.

In the last 30 years, C–C cross coupling reactions have become a reliable technique in organic synthesis due their versatility and efficiency. While drawbacks have been experienced on an industrial scale with the use of homogenous systems, many attempts have been made to facilitate a heterogeneous renaissance. Thus, this review gives an overview of the current status of the use of heterogeneous catalysts particularly in Suzuki and Heck reactions. Most recent developments focus on palladium immobilised or supported on various classes of supports, thus this review highlights and discuss contributions of the last decade.

We report upper limits on the Epoch of Reionization 21 cm power spectrum at redshifts 7.9 and 10.4 with 18 nights of data (∼36 hr of integration) from Phase I of the Hydrogen Epoch of Reionization Array (HERA). The Phase I data show evidence for systematics that can be largely suppressed with systematic models down to a dynamic range of ∼109 with respect to the peak foreground power. This yields a 95% confidence upper limit on the 21 cm power spectrum of Δ212≤(30.76)2mK2 at k = 0.192 h Mpc−1 at z = 7.9, and also Δ212≤(95.74)2mK2 at k = 0.256 h Mpc−1 at z = 10.4. At z = 7.9, these limits are the most sensitive to date by over an order of magnitude. While we find evidence for residual systematics at low line-of-sight Fourier k ∥ modes, at high k ∥ modes we find our data to be largely consistent with thermal noise, an indicator that the system could benefit from deeper integrations. The observed systematics could be due to radio frequency interference, cable subreflections, or residual instrumental cross-coupling, and warrant further study. This analysis emphasizes algorithms that have minimal inherent signal loss, although we do perform a careful accounting in a companion paper of the small forms of loss or bias associated with the pipeline. Overall, these results are a promising first step in the development of a tuned, instrument-specific analysis pipeline for HERA, particularly as Phase II construction is completed en route to reaching the full sensitivity of the experiment.

Palladium-catalyzed cross-coupling reactions have emerged as one of the most versatile tools in organic chemistry. Extensive efforts were made to adapt these reactions to aqueous media, not only for the purpose of environmental conservation but also to expand the scope, increase the efficiency and implement bio-compatible protocols. Among different palladium cross-coupling reactions, the Heck reaction turned out to be the most challenging in an aqueous environment. This led to various original developments in catalyst design. This review summarizes the different approaches pursued to perform Heck reactions in neat water as well as aqueous mixtures. Both, homogeneous and immobilized catalysts, including nanoparticles are presented herein. Graphical Abstract

We demonstrate that the chemical-feature model described in our original paper is distinguishable from the nongeneralizable models introduced by Chuang and Keiser. Furthermore, the chemical-feature model significantly outperforms these models in out-of-sample predictions, justifying the use of chemical featurization from which machine learning models can extract meaningful patterns in the dataset, as originally described.

The palladium-catalyzed Suzuki–Miyaura cross-coupling reaction of organic halides with boronic acids is one of the most versatile methods for the synthesis of biaryls. Green chemistry is a rapidly developing new field that provides us a proactive avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction medium. The technologies generated from such green chemistry endeavours may often be cheaper and more profitable. This review covers the literature on palladium-catalysed the Suzuki–Miyaura cross-coupling reaction in water. Graphical Abstract

Cu2O/Cu nanocatalyst was prepared by simple in situ gas phase H2O/O2 stimulating approach via deposition of Cu2O on the surface of Cu nanoparticles (NPs) using aqueous extract of papaya peel. The synthesized hybrid copper catalyst offers an efficient methodology for Pd-free Sonogashira and Chan–Lam cross-coupling reactions. A site-selective type catalytic activity was observed in Sonogashira coupling reaction by performing a controlled experiment using Cu (0) and the hybrid Cu2O/Cu nanocatalyst. It is characterized by solid UV-visible spectroscopy, Fourier transform infrared (FTIR spectroscopy), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). XRD and XPS analysis confirmed the formation of the Cu (0) and Cu2O NPs. The Cu2O/Cu NPs appear two different phases distributed like a lamellar sheet stacked one above the other. The presence of Cu2O phase in hybrid nano catalyst provides an attractive advantage highlighting a Cu (I)-Cu (0) synergistic interaction in the respective cross-coupling reaction.

The union of two powerful transformations, directed C–H activation and decarboxylative cross-coupling, for the enantioselective synthesis of vicinally functionalized alkyl, carbocyclic, and heterocyclic compounds is described. Starting from simple carboxylic acid building blocks, this modular sequence exploits the residual directing group to access more than 50 scaffolds that would be otherwise extremely difficult to prepare. The tactical use of these two transformations accomplishes a formal vicinal difunctionalization of carbon centers in a way that is modular and thus, amenable to rapid diversity incorporation. A simplification of routes to known preclinical drug candidates is presented along with the rapid diversification of an antimalarial compound series.

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis 1 – 4 . However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states 5 , 6 . Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity. Regularly separated nitrogen anchoring groups with delocalized π-bonding nature in a polymeric carbon nitride (PCN) host 7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density 8 . The adaptable coordination of individual Cu sites in GACs enables a cooperative bridge-coupling pathway through dynamic Cu–Cu bonding for diverse C–X (X = C, N, O, S) cross-couplings with a low activation barrier. In situ characterization and quantum-theoretical studies show that such a dynamic process for cross-coupling is triggered by the adsorption of two different reactants at geminal metal sites, rendering homo-coupling unfeasible. These intrinsic advantages of GACs enable the assembly of heterocycles with several coordination sites, sterically congested scaffolds and pharmaceuticals with highly specific and stable activity. Scale-up experiments and translation to continuous flow suggest broad applicability for the manufacturing of fine chemicals. Heterogeneous geminal-atom catalysts, which pair single-atom sites in specific coordination and spatial proximity, offer a new avenue for the sustainable manufacture of fine chemicals.

Insertion of palladium into an aryl halide bond is the first step in numerous variants of cross-coupling chemistry used to make carbon-carbon bonds. Copper is an appealing alternative catalyst for such reactions because of its abundance and downstream reactivity profile. However, this preliminary step, termed oxidative addition, is often prohibitively slow for the cheaper metal. Le et al. report a photocatalytic way around this problem. A photoredox catalyst paired with a silane can activate aryl bromides to react with copper, likely via aryl radicals. The copper in this case then catalyzes trifluoromethylation of the arenes. Science , this issue p. 1010 A photocatalyst and silane combination activates aryl bromides toward functionalization by copper catalysis. Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.