Most of today's use of transition metal-catalyzed cross-coupling chemistry relies on expensive quantities of palladium (Pd). Here we report that nanoparticles formed from inexpensive FeCl3 that naturally contains parts-per-million (ppm) levels of Pd can catalyze Suzuki-Miyaura reactions, including cases that involve highly challenging reaction partners. Nanomicelles are employed to both solubilize and deliver the reaction partners to the Fe-ppm Pd catalyst, resulting in carbon-carbon bond formation. The newly formed catalyst can be isolated and stored at ambient temperatures. Aqueous reaction mixtures containing both the surfactant and the catalyst can be recycled.
Hold me close: Highly enantioselective catalysis of tandem acetalization/cycloisomerization reactions of o‐alkynylbenzaldehydes has been achieved using gold complexes of chiral acyclic diaminocarbene ligands that have electron‐deficient aryl substituents. X‐ray crystallography and DFT calculations implicate weak gold‐arene interactions—absent in the case of simple phenyl substituents—that define the chirality of the substrate binding site.
An overview is presented on the unfortunate use of organic solvents as the traditional medium in which organic synthesis has been, and continues to be, practiced. An argument is made, from the environmental perspective, for a long overdue switch to alternative reaction media, and water in particular, following Nature's lead.
A new monophosphine ligand, HandaPhos, has been identified that when complexed in a 1:1 ratio with Pd(OAc)2, forms a catalyst that is generally useful, enabling Pd-catalyzed cross-couplings to be run using ≤1000 ppm of this catalyst. Applications to heavily utilized Suzuki-Miyaura reactions involving highly funtionalized reaction partners are demonstrated, all run in the absence of organic solvents using environmentally benign nanoparticle reactors in water at ambient temperatures. Comparisons with existing state-of-the-art ligands and catalysts are discussed herein.
As a result of a unique synergy between ligand-free Fe/ppm Pd nanoparticles and PEG-containing designer surfactants, a facile and selective reduction of nitro-containing aromatics and heteroaromatics can be effected in water at room temperature in the presence of NaBH4 . This new nanotechnology involves low catalyst loadings, is highly chemoselective, and tolerates a wide variety of functional groups. The process, which includes recycling of the entire aqueous medium, offers a general, environmentally responsible, and notably safe approach to highly valued reductions of nitro-containing compounds.
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