The new monophosphine ligand HandaPhos has been identified such that when complexed in a 1:1 ratio with Pd(OAc)₂, enables Pd-catalyzed cross-couplings to be run using ≤1000 ppm of this pre-catalyst. Applications to Suzuki–Miyaura reactions involving highly funtionalized reaction partners are demonstrated, all run using environmentally benign nanoreactors in water at ambient temperatures. Comparisons with existing state-of-the-art ligands and catalysts are discussed herein.

The new monophosphine ligand HandaPhos has been identified such that when complexed in a 1:1 ratio with Pd(OAc)₂, enables Pd-catalyzed cross-couplings to be run using ≤1000 ppm of this pre-catalyst. Applications to Suzuki–Miyaura reactions involving highly funtionalized reaction partners are demonstrated, all run using environmentally benign nanoreactors in water at ambient temperatures. Comparisons with existing state-of-the-art ligands and catalysts are discussed herein.

Nickel nanoparticles, formed in situ and used in combination with micellar catalysis, catalyze Suzuki–Miyaura cross-couplings in water under very mild reaction conditions.

Nickel nanoparticles, formed in situ and used in combination with micellar catalysis, catalyze Suzuki–Miyaura cross-couplings in water under very mild reaction conditions.

Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles gives good to excellent ee’s of product lactones. In-flask product isolation, along with the recycling of the catalyst and the reaction medium, are combined to arrive at an especially environmentally friendly process.

Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles gives good to excellent ee’s of product lactones. In-flask product isolation, along with the recycling of the catalyst and the reaction medium, are combined to arrive at an especially environmentally friendly process.

Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology.

On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β-ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors.

Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology.

The addition of NaBH₄ to Pd(OAc)₂ in water containing nanomicelles leads to the generation of H₂ and Pd nanoparticles. Subsequent reduction of disubstituted alkynes affords Z-alkenes in high yields. These reactions are general, take place in water at ambient temperatures, and offer recycling of the aqueous reaction mixture along with low overall E Factors.

On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β-ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors.

The addition of NaBH₄ to Pd(OAc)₂ in water containing nanomicelles leads to the generation of H₂ and Pd nanoparticles. Subsequent reduction of disubstituted alkynes affords Z-alkenes in high yields. These reactions are general, take place in water at ambient temperatures, and offer recycling of the aqueous reaction mixture along with low overall E Factors.

Transition-metal-catalyzed carbon–carbon and carbon–heteroatom bond formations are among the most heavily used types of reactions in both academic and industrial settings. As important as these are to the synthetic community, such cross-couplings come with a heavy price to our environment, and sustainability. E Factors are one measure of waste created, and organic solvents, by far, are the main contributors to the high values associated, in particular, with the pharmaceutical and fine-chemical companies which utilize these reactions. An alternative to organic solvents in which cross-couplings are run can be found in the form of micellar catalysis, wherein nanoparticles composed of newly introduced designer surfactants enable the same cross-couplings, albeit in water, with most taking place at room temperature. In the absence of an organic solvent as the reaction medium, organic waste and hence, E Factors, drop dramatically.

Die übergangsmetallkatalysierte Bildung von Kohlenstoff-Kohlenstoff- oder Kohlenstoff-Heteroatom-Bindungen gehört zu den am intensivsten genutzten Reaktionen in der universitären und industriellen Chemie. So bedeutend solche Kreuzkupplungen für die Synthese sind, so hoch ist auch ihr Preis für Umwelt und Nachhaltigkeit. Ein Instrument, um die Menge an Lösungsmittelabfall zu messen, ist der E-Faktor. Ursächlich für einen hohen E-Faktor bei der Produktion von Pharmazeutika und Feinchemikalien sind vor allem die verwendeten organischen Lösungsmittel. Eine Alternative zu organischen Lösungsmitteln bei Kreuzkupplungen bietet die Katalyse mit Micellen. Bei diesem Verfahren katalysieren neuartige Nanopartikel aus Designer-Tensiden die Reaktion, die in wässriger Umgebung und zumeist bei Raumtemperatur abläuft. Da ohne organisches Lösungsmittel auch kein organischer Abfall produziert wird, reduziert sich der E-Faktor drastisch.

Using the newly introduced designer surfactant polyethylene glycol ubiquinol sebacate (PQS), as the platform for micellar catalysis, non-racemic BINAP has been covalently attached and rhodium(I) inserted to form PQS-BINAP-Rh. This species, the first example of a non-racemically-ligated transition metal catalyst-tethered amphiphile, can be utilized for Rh-catalyzed asymmetric conjugate addition reactions of arylboronic acids to acyclic and cyclic enones. These are performed in water at room temperature, while the catalyst can be recycled without its removal from water in the reaction vessel.

New technology for palladium-catalyzed cross-couplings between B₂pin₂ and aryl bromides leading to arylboronates is described. Micellar catalysis serves to enable borylations to take place in water as the only medium at ambient temperatures.

Screening of different sources of Pd/C shows reagents of highly variable nanoparticle sizes and oxidation states of the metal. Typically, catalysts with higher surface area are viewed as likely to be the more reactive. In this paper a new form of Pd/C, “UC Pd” is described that is shown to contain larger nanoparticles yet it is the most reactive catalyst of those sold commercially for Sonogashira coupling reactions. UC Pd functions efficiently in the absence of a copper co-catalyst, under very mild and “green” conditions using inexpensive 95 % EtOH at 50 °C. It is also the only form of Pd/C that can be recycled. In side-by-side reactions with several commercially available forms of Pd/C, none compete successfully with UC Pd under standardized conditions. Physical data obtained from extensive surface analysis using TEM, XRD, XPS, and CO-TPD measurements lead to an explanation behind the unique reactivity of this new recyclable form of Pd/C.

Copper-in-charcoal (Cu/C) is an effective heterogeneous catalyst for tandem diazo transfer/click reactions. In the presence of Cu/C, various azides can be generated in situ from the corresponding amines, and subsequently undergo [3+2] cycloaddition with terminal alkynes to afford triazoles in good yields. The catalyst is also easily recycled.

Unsymmetrical di- and triarylamines can be formed under green chemistry conditions, taking advantage of micellar catalysis leading to palladium-catalyzed aminations at ambient temperatures in water as the only medium.

Simply mixing a water-insoluble diolefinic substrate and Grubbs second generation catalyst in pure water containing small amounts of the amphiphile polyoxyethanyl α-tocopheryl sebacate (PTS) leads to efficient ring-closing metathesis.