/pdf/advances-in-transition-metal-pd-ni-fe-catalyzed-cross-46kfk7jmlm.pdf

Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners.

Cross-coupling reactions using Pd-NHC (NHC = N-heterocyclic carbene) catalysts are discussed in this critical review and examined in terms of catalytic activity and how these have permitted advances in the area as they developed (95 references).

N-Heterocyclic carbene (NHC) ligands and palladium in homogeneous cross-coupling catalysis: a perfect union

Intermolecular dehydrogenative Heck reactions.

The E factor 25 years on: the rise of green chemistry and sustainability

Traditional organic synthesis relies heavily on organic solvents for a multitude of tasks, including dissolving the components and facilitating chemical reactions, because many reagents and reactive species are incompatible or immiscible with water. Given that they are used in vast quantities as compared to reactants, solvents have been the focus of environmental concerns. Along with reducing the environmental impact of organic synthesis, the use of water as a reaction medium also benefits chemical processes by simplifying operations, allowing mild reaction conditions, and sometimes delivering unforeseen reactivities and selectivities. After the “watershed” in organic synthesis revealed the importance of water, the development of water-compatible catalysts has flourished, triggering a quantum leap in water-centered organic synthesis. Given that organic compounds are typically practically insoluble in water, simple extractive workup can readily separate a water-soluble homogeneous catalyst as an aqueous so...

Catalytic Organic Reactions in Water toward Sustainable Society

An environmentally benign surfactant (TPGS-750-M), a diester composed of racemic α-tocopherol, MPEG-750, and succinic acid, has been designed and readily prepared as an effective nanomicelle-forming species for general use in metal-catalyzed cross-coupling reactions in water. Several “name” reactions, including Heck, Suzuki−Miyaura, Sonogashira, and Negishi-like couplings, have been studied using this technology, as have aminations, C−H activations, and olefin metathesis reactions. Physical data in the form of DLS and cryo-TEM measurements suggest that particle size and shape are key elements in achieving high levels of conversion and, hence, good isolated yields of products. This new amphiphile will soon be commercially available.

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TPGS-750-M: a second-generation amphiphile for metal-catalyzed cross-couplings in water at room temperature.

Mix in water, stir. That is all that is required in this new approach to sp(3)-sp(2) cross-couplings between an alkyl iodide and an aryl bromide, both potentially bearing functionality. They react under catalysis by Pd(0) in the presence of zinc powder, aided by a nonionic amphiphile, to give the alkylated aromatic. No organic solvents and no heating; just add water.

Arkady Krasovskiy

Papers

TPGS-750-M: a second-generation amphiphile for metal-catalyzed cross-couplings in water at room temperature.

Zn-mediated, Pd-catalyzed cross-couplings in water at room temperature without prior formation of organozinc reagents.

Stereoselective Negishi-like Couplings Between Alkenyl and Alkyl Halides in Water at Room Temperature

Cross-couplings between benzylic and aryl halides “on water”: synthesis of diarylmethanes

Organozinc Chemistry Enabled by Micellar Catalysis. Palladium-Catalyzed Cross-Couplings between Alkyl and Aryl Bromides in Water at Room Temperature.