Ligand-Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands.

Herein, we developed the recyclable ligand-free iridium (Ir)-hydride based Ir0 nanoparticles (NPs) for the first regioselective partial hydrogenation of PV -substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal-surface-bound hydrides, most likely formed from Ir0 species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High-resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X-ray photoelectron spectroscopy confirmed the dominance of Ir0 in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (H8 -BINAP) and its derivatives without losing enantioselectivity during catalytic events.

Micelle-Enabled Photoassisted Selective Oxyhalogenation of Alkynes in Water under Mild Conditions.

Using micelles of FI-750-M, visible light, photocatalysts, and inexpensive halogenating reagents, such as N-bromosuccinimide and N-chlorosuccinimde, selective oxyhalogenations of alkynes were achieved in water under very mild conditions. No halogenation at the aromatic rings was detected, and control experiments revealed the radical pathway. The easily conducted protocol exhibited high reproducibility, was readily adjusted to gram scale, and allowed for recycling of reaction medium and catalyst.

Recyclable cellulose-palladium nanoparticles for clean cross-coupling chemistry.

Cheap, recyclable, and robust cellulose-palladium nanoparticles were developed and fully characterized by FTIR, TEM, XPS, TGA, and NMR. The nanoparticles enabled cross-coupling chemistry in a truly general fashion i.e., Suzuki-Miyaura, Heck, Sonogashira, and C-H activation. Notably, all types of transformations were achieved with a single type of nanocatalyst. Complete recyclability of the catalyst and low traces of palladium in the product demonstrates the greenness of the protocol.

Competing amination and C-H arylation pathways in Pd/xantphos-catalyzed transformations of binaphthyl triflates: switchable routes to chiral amines and helicene derivatives.

A Pd(OAc)2/xantphos catalyst system was found effective for benzylaminations of binaphthyl 2-triflates bearing a variety of alkyl, benzyl, and substituted phenyl substituents at the 2'-position. With 2'-aryl substituents, an intramolecular Pd-catalyzed C-H arylation was observed as a competing side reaction under some conditions. By adjusting the solvent and quantity of the amine, the reaction was optimized to favor either the amination or the C-H arylation pathway, affording two distinct and potentially useful sets of products. The amines represent tunable chiral ligand precursors, while the C-H arylation pathway affords a series of benzofused [5]helicene derivatives. Kinetic studies and activation parameters for the C-H arylation pathway, supported by DFT calculations, are consistent with a concerted metalation-deprotonation (CMD) mechanism involving a Pd-bound carbonate as the base. Xantphos is proposed to facilitate the turnover-limiting inner-sphere CMD step by acting as a hemilabile ligand, while its wide bite angle engenders a low reductive elimination barrier.

Safe and Selective Nitro Group Reductions Catalyzed by Sustainable and Recyclable Fe/ppm Pd Nanoparticles in Water at Room Temperature.

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.

HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium-Catalyzed Cross-Couplings in Water at Room Temperature.

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.

Ligand- and Brønsted acid/base-switchable reaction pathways in gold(I)-catalyzed cycloisomerizations of allenoic acids.

Gold-promoted cyclizations of 2,2-diaryl substituted γ-allenoic acids were found to give three isomeric lactone products, each of which could be obtained selectively by exploiting Brønsted acid/base and ligand effects. Simple 5-exo-trig cyclization products were favored by strong donor ligands or base additives, whereas weak donor ligands and a Brønsted acid additive gave isomeric enelactones resulting from double bond migration. Further optimization afforded a class of medicinally relevant bridged tricyclic lactones via a tandem hydroacyloxylation/hydroarylation process. Kinetic studies and control experiments indicated that the initial 5-exo-trig cyclization product serves as a branch point for further isomerization to the other lactone products via cooperative gold(I)/Brønsted acid catalysis.

Nanonickel-catalyzed Suzuki-Miyaura cross-couplings in water.

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

Aerobic oxidation in nanomicelles of aryl alkynes, in water at room temperature.

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 ß-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.

Asymmetric gold-catalyzed lactonizations in water at room temperature.

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.

Aqueous Micelles as Solvent, Ligand, and Reaction Promoter in Catalysis.

Water is considered to be the most sustainable and safest solvent. Micellar catalysis is a significant contributor to the chemistry in water. It promotes pathways involving water-sensitive intermediates and transient catalytic species under micelles' shielding effect while also replacing costly ligands and dipolar-aprotic solvents. However, there is a lack of critical information about micellar catalysis. This includes why it works better than traditional catalysis in organic solvents, why specific rules in micellar catalysis differ from those of conventional catalysis, and how the limitations of micellar catalysis can be addressed in the future. This Perspective aims to highlight the current gaps in our understanding of micellar catalysis and provide an analysis of designer surfactants' origin and essential components. This will also provide a fundamental understanding of micellar catalysis, including how aqueous micelles can simultaneously perform multiple functions such as solvent, ligand, and reaction promoter.

Access to 2'-substituted binaphthyl monoalcohols via complementary nickel-catalyzed Kumada coupling reactions under mild conditions: key role of a P,O ligand.

Two complementary Kumada coupling methods for the conversion of monotriflated 1,1'-binaphthalene-2,2'-diol (BINOL) into 2'-substituted binaphthyl monoalcohols under mild conditions are reported. A protocol using NiCl2(dppe), in combination with an improved preparation of the monotriflate, is effective for 1,1'-binaphthalene-2-ols containing unsubstituted or electron-poor aryl or benzyl 2'-substituents. An alternative procedure, using a potentially hemilabile-bidentate phosphinan-4-ol ligand, is superior for products containing neopentyl or electron-rich aryl 2'-substituents. The obtained binaphthyl alcohols represent potentially useful synthons for chiral ligands and auxiliaries.

Aqueous micellar technology: an alternative beyond organic solvents.

Solvents are the major source of chemical waste from synthetic chemistry labs. Growing attention to more environmentally friendly sustainable processes demands novel technologies to substitute toxic or hazardous solvents. If not always, sometimes, water can be a suitable substitute for organic solvents, if used appropriately. However, the sole use of water as a solvent remains non-practical due to its incompatibility with organic reagents. Nonetheless, over the past few years, new additives have been disclosed to achieve chemistry in water that also include aqueous micelles as nanoreactors. Although one cannot claim micellar catalysis to be a greener technology for every single transformation, it remains the sustainable or greener alternative for many reactions. Literature precedents support that micellar technology has much more potential than just as a reaction medium, i.e., the role of the amphiphile as a ligand obviating phosphine ligands in catalysis, the shielding effect of micelles to protect water-sensitive reaction intermediates in catalysis, and the compartmentalization effect. While compiling the powerful impact of micellar catalysis, this article highlights two diverse recent technologies: (i) the design and employment of the surfactant PS-750-M in selective catalysis; (ii) the use of the semisynthetic HPMC polymer to enable ultrafast reactions in water.

Ultrasmall CuI Nanoparticles Stabilized on Surface of HPMC: An Efficient Catalyst for Fast and Organic Solvent-Free Tandem Click Chemistry in Water.

A simple and environmentally benign technology for synthesizing ultrasmall CuI nanoparticles (NPs) on the surface of the food additive hydroxypropyl methylcellulose (HPMC) and their application in completely organic solvent-free tandem alkyne-azide cycloaddition reactions were reported. The NP catalyst was thoroughly characterized by high-angle annular dark-field scanning transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis for its morphology, particle size distribution, chemical composition, and oxidation state analyses. The NP catalyst was highly efficient, affording products in 10-45 min. All products were obtained in high purity by simple filtration, obviating organic solvents from the reaction set-up to product isolation. The methodology is general and scalable as validated by a broad substrate scope.

Metal-Micelle Interaction Leading to Spontaneous Formation of Ligand-Free Palladium(0) Nanoparticles: Highly Efficient Catalysis Enabling Biaryl Ketone Formation from Carboxylic Acid Derivatives.

A novel strategy has been developed to spontaneously form ligand-free Pd(0) nanoparticles (NPs) from water- and air-sensitive Pd2dba3 in water. These NPs are thoroughly characterized by IR, NMR, and mass spectrometry, revealing that the metal-micelle binding plays a critical role in their stability and activity. High-resolution transmission electron microscopy supported the ultrasmall nature of NPs, whereas X-ray photoelectron spectroscopy analysis confirmed the zero-oxidation state of Pd. The shielding effect of micelles and enhanced stability of NPs enabled fast cross-couplings of water-sensitive triazine adducts of carboxylic acid to form nonsymmetrical biaryl ketones. These naturally formed NPs are more efficient than new synthetic NPs formed under a hydrogen atmosphere and traditional NPs formed using the air-sensitive Grignard reagent as a reductant. The activity of naturally formed NPs is compared with that of synthetic NPs over 34 substrates, revealing that naturally formed NPs are much more efficient than synthetic NPs.

Phosphine Ligand-Free Bimetallic Ni(0)Pd(0) Nanoparticles as a Catalyst for Facile, General, Sustainable, and Highly Selective 1,4-Reductions in Aqueous Micelles.

Phosphine ligand-free bimetallic nanoparticles (NPs) composed of Ni(0)Pd(0) catalyze highly selective 1,4-reductions of enones, enamides, enenitriles, and ketoamides under aqueous micellar conditions. A minimal amount of Pd (Ni/Pd = 25:1) is needed to prepare these NPs, which results in reductions without impacting N- and O-benzyl, aldehyde, nitrile, and nitro functional groups. A broad range of substrates has been studied, including a gram-scale reaction. The metal-micelle binding is supported by surface-enhanced Raman spectroscopy data on both the NPs and their individual components. Optical imaging, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy analyses reveal the formation of NP-containing micelles or vesicles, NP morphology, particle size distribution, and chemical composition. X-ray photoelectron spectroscopy measurements indicate the oxidation state of each metal within these bimetallic NPs.

Metal-Micelle Cooperativity: Phosphine Ligand-Free Ultrasmall Palladium(II) Nanoparticles for Oxidative Mizoroki-Heck-type Couplings in Water at Room Temperature.

The amphiphile PS-750-M generates stable, phosphine ligand-free, and catalytically active ultrasmall Pd(II) nanoparticles (NPs) from Pd(OAc)2, preventing their precipitation, polymerization, and oxidation state changes. PS-750-M directly interacts with Pd(II) NP surfaces, as confirmed by high-resolution mass spectrometry and IR spectroscopy, resulting in their high stability. The Pd cations in NPs are most likely held together by hydroxides and acetate ions. The NPs were characterized by HRTEM, revealing their morphology and particle size distribution, and by HRMS and IR, providing evidence for NP-amphiphile interaction. The NP catalytic activity was examined in the context of oxidative Mizoroki-Heck-type couplings in water at room temperature. Hot filtration, hot extraction, and three-phase tests indicate heterogeneous catalysis occurring at the micellar interface rather than homogeneous catalysis occurring in the solution. NMR studies indicate that the catalytic activity stems from metal cation-π interactions of the styrene along with transmetalation by the arylboronic acid, followed by insertion and ß-H elimination to furnish the coupled product along with the reoxidation of Pd by benzoquinone to complete the catalytic cycle. This method is very mild and sustainable, both in terms of NP synthesis and subsequent catalysis, and shows broad substrate scope while circumventing the need for organic solvents for this important class of couplings.

Photoassisted Charge Transfer Between DMF and Substrate: Facile and Selective N,N-Dimethylamination of Fluoroarenes.

A reversible Van der Waals complex formation between the electron-deficient fluorinated aromatic ring and N,N-dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C-N bond. Control experiments revealed that the simultaneous SN Ar pathway also contributes to product formation. This methodology is mild, metal-free, and effective for the amination of a variety of substrates. The reproducibility of this methodology was also verified on gram-scale reactions. The CT states were supported by control UV/Vis spectroscopy and computational studies.

Shielding Effect of Nanomicelles: Stable and Catalytically Active Oxidizable Pd(0) Nanoparticle Catalyst Compatible for Cross-Couplings of Water-Sensitive Acid Chlorides in Water.

Under the shielding effect of nanomicelles, a sustainable micellar technology for the design and convenient synthesis of ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) and their subsequent catalytic exploration for couplings of water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays a crucial role in stabilizing these NPs, preventing their aggregation and oxidation state changes. These NPs were characterized using 13C nuclear magnetic resonance (NMR), infrared (IR), and surface-enhanced Raman scattering (SERS) spectroscopy to evaluate the carbonyl interactions of PS-750-M with Pd. High-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDX) studies were performed to reveal the morphology, particle size distribution, and chemical composition, whereas X-ray photoelectron spectroscopy (XPS) measurements unveiled the oxidation state of the metal. In the cross-couplings of water-sensitive acid chlorides with boronic acids, the micelle's shielding effect and boronic acids plays a vital role in preventing unwanted side reactions, including the hydrolysis of acid chlorides under basic pH. This approach is scalable and the applications are showcased in multigram scale reactions.

Fast Amide Couplings in Water: Extraction, Column Chromatography, and Crystallization Not Required.

In the micelle of PS-750-M, the presence of 3° amides from the surfactant proline linker mimics dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. The resultant micellar properties enable extremely fast amide couplings mediated by 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (without hydroxybenzotriazole), rather than expensive and specialized coupling agents. Conditions have been developed wherein products precipitate, and isolation by filtration completely avoids the use of organic solvent. This methodology is scalable and avoids product epimerization.