Sustainable Fe–ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water

Handa, Sachin; Wang, Ye; Gallou, Fabrice; Lipshutz, Bruce H.

doi:10.1126/science.aac6936

Cited by 297 publications

(249 citation statements)

References 38 publications

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“…A new iron‐based platform for NP formation has been developed, originating from methyl Grignard reduction of FeCl 3 in THF at room temperature in the presence of the ligand SPhos . When this source of iron(III) contains enough native palladium (i.e., as an “impurity”), conversion to the derived Fe/ppm Pd NPs leads to a catalyst capable of mediating SM couplings in aqueous nanomicelles at between room temperature and 45 °C.…”

Section: Spotlight On Pd Catalysismentioning

confidence: 99%

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Lipshutz

Ghorai²,

Cortes‐Clerget

2018

Chemistry A European J

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305

182

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Recent developments over the past few years in aqueous micellar catalysis are discussed. Applications to problems in synthesis are highlighted, enabled by the use of surfactants that self-aggregate in water into micelles as nanoreactors. These include amphiphiles that have been available for some time, as well as those that have been newly designed. Reactions catalyzed by transition metals, including Pd, Cu, Rh, and Au, are of particular focus.

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Section: Spotlight On Pd Catalysismentioning

confidence: 99%

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Lipshutz

Ghorai²,

Cortes‐Clerget

2018

Chemistry A European J

Self Cite

305

182

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“…Since, majority of the chemical wastes from a reaction mixture corresponds to the solvents. Therefore, the use of water as a reaction medium, which is considered a benign solvent due to its natural abundance and physiological compatibility, may potentially contribute towards the serious efforts of reducing the environmental impacts of the organic reactions [47]. In this study, the catalytic activity of the as-synthesized PG-HRG-Pd-1 nanocatalyst was evaluated in the Suzuki Miyaura coupling of bromobenzene with phenylboronic acid in water.…”

Section: Suzuki Reaction Catalyzed By Pd@graphene Nanocatalystmentioning

confidence: 99%

Plant Extract Mediated Eco-Friendly Synthesis of Pd@Graphene Nanocatalyst: An Efficient and Reusable Catalyst for the Suzuki-Miyaura Coupling

et al. 2017

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Suzuki-Miyaura coupling reaction catalyzed by the palladium (Pd)-based nanomaterials is one of the most versatile methods for the preparation of biaryls. However, use of organic solvents as reaction medium causes a big threat to environment due to the generation of toxic byproducts as waste during the work up of these reactions. Therefore, the use of water as reaction media has attracted tremendous attention due to its environmental, economic, and safety benefits. In this study, we report on the synthesis of green Pd@graphene nanocatalyst based on an in situ functionalization approach which exhibited excellent catalytic activity towards the Suzuki-Miyaura cross-coupling reactions of phenyl halides with phenyl boronic acids under facile conditions in water. The green and environmentally friendly synthesis of Pd@graphene nanocatalyst (PG-HRG-Pd) is carried out by simultaneous reduction of graphene oxide (GRO) and PdCl 2 using Pulicaria glutinosa extract (PGE) as reducing and stabilizing agent. The phytomolecules present in the plant extract (PE) not only facilitated the reduction of PdCl 2 , but also helped to stabilize the surface of PG-HRG-Pd nanocatalyst, which significantly enhanced the dispersibility of nanocatalyst in water. The identification of PG-HRG-Pd was established by various spectroscopic and microscopic techniques, including, high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy. The as-prepared PG-HRG-Pd nanocatalyst demonstrated excellent catalytic activity towards the Suzuki-Miyaura cross coupling reactions under aqueous, ligand free, and aerobic conditions. Apart from this the reusability of the catalyst was also evaluated and the catalyst yielded excellent results upon reuse for several times with marginal loss of its catalytic performance. Therefore, the method developed for the green synthesis of PG-HRG-Pd nanocatalyst and the eco-friendly protocol used for the Suzuki coupling offers a mild and effective substitute to the existing protocols and may significantly contribute to the endeavors of green chemistry.

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“…Though boron reagents applicable for carbon–boron bond formation in water are known 22,23 , their biocompatibility, cell permeability, stability, and reactivity in living systems, where biomolecules, nucleic acids, and metal ions abound, are uncertain. Nevertheless, since boron reagents designed for in vivo chemical biology applications are precedented 24–26 , we reasoned that reagents suitable for biological borylation could be found.…”

mentioning

confidence: 99%

Genetically programmed chiral organoborane synthesis

Kan

Huang

Gumulya

et al. 2017

Nature

260

213

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Summary paragraph Recent advances in enzyme engineering and design have expanded nature’s catalytic repertoire to functions that are new to biology1–3. Yet only a subset of these engineered enzymes can function in living systems4–7. Finding enzymatic pathways that forge chemical bonds not found in biology is particularly difficult in the cellular environment, as this hinges on the discovery not only of new enzyme activities but also reagents that are simultaneously sufficiently reactive for the desired transformation and stable in vivo. Here we report the discovery, evolution, and generalisation of a fully genetically-encoded platform for producing chiral organoboranes in bacteria. Escherichia coli harbouring wild-type cytochrome c from Rhodothermus marinus8 (Rma cyt c) were found to form carbon–boron bonds in the presence of borane-Lewis base complexes, through carbene insertion into B–H bonds. Directed evolution of Rma cyt c in the bacterial catalyst provided access to 16 novel chiral organoboranes. The catalyst is suitable for gram scale biosynthesis, offering up to 15300 turnovers, 6100 h–1 turnover frequency, 99:1 enantiomeric ratio (e.r.), and 100% chemoselectivity. The enantio-preference of the biocatalyst could also be switched to provide either enantiomer of the organoborane products. Evolved in the context of whole-cell catalysts, the proteins were more active in the whole-cell system than in purified forms. This study establishes a DNA-encoded and readily engineered bacterial platform for borylation; engineering can be accomplished at a pace which rivals the development of chemical synthetic methods, with the ability to achieve turnovers that are two orders of magnitude (over 400-fold) greater than that of known chiral catalysts for the same class of transformation9–11. This tunable method for manipulating boron in cells opens a whole new world of boron chemistry in living systems.

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Sustainable Fe–ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water

Cited by 297 publications

References 38 publications

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Plant Extract Mediated Eco-Friendly Synthesis of Pd@Graphene Nanocatalyst: An Efficient and Reusable Catalyst for the Suzuki-Miyaura Coupling

Genetically programmed chiral organoborane synthesis

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