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We synthesized N , N -dimethylformamide (DMF)-stabilized manganese nanoparticles (Mn NPs) in a one-step process under air using manganese(ii) chloride as the precursor. The Mn NPs were characterized in terms of particle size, oxidation state, and local structure using annular dark-field scanning transmission electron microscopy (ADF-STEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). The results indicate that Mn NPs are divalent nanosized particles with Mn-O bonds. The Mn NPs exhibited high catalytic activity, achieving a turnover number (TON) of 15 800, surpassing previous manganese catalysts in alkene hydrosilylation. Furthermore, the Mn NPs maintained their catalytic activity after the reaction, enabling multiple recycling., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Metal nanoclusters (NCs) have unique properties because of their small size, which makes them useful as catalysts in reactions like cross-coupling. Pd-catalyzed oxidative amination, which involves dehydrogenative C-N bond formation, uses Pd complexes as the active species. It is known that the catalytic conditions involve the formation of Pd(0) species from Pd NCs, but the precise role of Pd NCs in the transformations has not been established. In this study, we investigated the characteristic properties of Pd NCs in oxidative amination of 1,3-dienes. The reaction achieved direct amination of commercially accessible 1,3-dienes with secondary aromatic amines, providing a variety of nitrogen containing 1,3-dienes. The compound was applicable to radical polymerization to provide the nitrogen-fabricated 1,3-diene-based polymer, which exhibited a different thermal stability compared to aliphatic nitrogen-fabricated diene polymers. In addition to the synthetic utility, by combining X-ray absorption fine structure and small-angle X-ray scattering analysis, we revealed amines and 1,3-dienes affected metal leaching from the Pd nanoparticles and stabilization of Pd NCs in the catalytic reaction. Additionally, DFT calculation suggested that the catalytic intermediate contained multiple adjacent Pd atoms and was responsible for formation of an σ-allylic intermediate that is difficult to form with the use of Pd complexes. These results could be used to understand the underlying phenomenon in the oxidative coupling reaction and develop Pd NCs-based dehydrogenation.

α-Alkylation reactions between amides and alcohols, with dimethylacetamide-stabilized Ru nanoparticles (NPs) as the catalyst, were investigated. The reactions proceeded with low catalyst loadings compared to metal complexes. Characterizations of the Ru NPs were performed by X-ray photoelectron spectroscopy, X-ray absorption fine structure spectroscopy, and various techniques. Control experiments revealed the reaction mechanisms, which proceeded via hydrogen autotransfer with alcohols.

N , N -Dimethylformamide-stabilized Ru nanoparticles (NPs) provide a highly efficient catalyst for the Guerbet reaction of primary alcohols. DMF-modified Ru NPs were synthesized, and characterized by transition electron microscopy, and X-ray absorption spectroscopy, X-ray photoelectronspectroscopy, and Fourier-transform infrared spectroscopy. The Ru NP catalyst was highly durable during catalytic reactions under external additive/solvent-free conditions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A regioselective and Z-selective three-component silylalkoxylation of 1,3-diene using various alcohols, disilane, and a catalytic Pd/Cu/1,4-benzoquinone/O 2 system is established in this Letter. The reaction generates tetra-substituted allyl silanes containing allyl ether moieties in up to 80% isolated yield and on a 1-10 mmol scale via oxidative coupling. A wide variety of substrates, including benzyl alcohol derivates, aliphatic alcohols, and bioactive compounds such as cholesterol, are suitable for use in the developed reaction system.

Ti-Pd alloy catalysts were developed for the cross β-arylmethylation between arylmethylalcohols and different primary alcohols via a hydrogen autotransfer mechanism. The alloy catalysts could be reused multiple times without the need for pre-activation. Analysis of the reaction solution by inductively coupled plasma atomic absorption spectroscopy indicated that only a minimal amount of Ti and no Pd was leached from the catalyst.

We report N,N-dimethylformamide-stabilised Pd nanoparticle (Pd NP)-catalysed transfer vinylation of alcohols from vinyl ether. Pd NPs combined with bathophenanthroline exhibited high catalytic activity. This reaction proceeded with low catalyst loading and the catalyst remained effective even after many rounds of recycling. The observation of the catalyst using transmission electron microscopy and dynamic light scattering implied no deleterious aggregation of Pd NPs.

The first successful example of a catalytic enantioselective intramolecular Tishchenko reaction of a meso -dialdehyde in the presence of a chiral iridium complex is described. Chiral lactones were obtained in good yields with up to 91% ee. The obtained enantioenriched lactones were utilized for the first synthesis of ( S )-cedarmycins A and B., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A highly regioselective and stereoselective difunctionalization reaction of 1,3-diene with amine and disilane to form C-N and C-Si bonds via a one-step Pd/Cu/O 2 system is disclosed. The difunctionalization reaction affords allylic silanes, including the allylic amine moiety, in up to 92 % yield in the absence of any acid, base, or external ligand. The developed synthetic methodology can be scaled to 100 g in high yield with high Z-selectivity, which demonstrates the feasibility of the reaction for industrial applications., (© 2021 Wiley-VCH GmbH.)

A simple method for the cross β-alkylation of linear alcohols with benzyl alcohols in the presence of DMF-stabilized iridium nanoparticles was developed. The nanoparticles were prepared in one-step and thoroughly characterized. Furthermore, the optimum reaction conditions have a wide substrate scope and excellent product selectivity.

The development of a C2-extension of primary alcohols with ethanol as the C2 source and catalysis by [Cp*IrCl 2 ] 2 (where Cp* = pentamethylcyclopentadiene) is described. This new extension system was used for a range of benzylic alcohol substrates and for aliphatic alcohols with ethanol as an alkyl reagent to generate the corresponding C2-extended linear alcohols. Mechanistic studies of the reaction by means of intermediates and deuterium labeling experiments suggest the reaction is based on hydrogen autotransfer.

Herein, the synthesis of new N , N -dimethylformamide (DMF)-protected palladium nanoparticles (Pd NPs-OAc) employing Pd (OAc) 2 (= Pd(OCOCH 3 ) 2 ) as the NP precursor is reported. Pd NPs-OAc were comprehensively characterized by transmission electron microscopy, FT-IR, NMR, and X-ray photoelectron spectroscopy to determine the Pd NP size distribution and the coordination state of DMF. Pd NPs-OAc were compared with Pd NPs-Cl, using PdCl 2 as the NP precursor. The Suzuki-Miyaura cross-coupling reaction proceeded efficiently in the presence of Pd NPs-OAc and a high catalytic activity was observed with a turnover number of up to 1.5 × 10 5 . Furthermore, the Pd NP-OAc catalysts could be recycled at least five times., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

In this mini-review, we summarize the solution syntheses of N , N -dimethylformamide (DMF)-protected metal nanoparticles (NPs) and nanoclusters (NCs) and their use in catalytic reactions. Representative examples are given of external-stabilizer/protectant-free metal NP and NC syntheses by reduction with DMF. In this method, DMF has three roles, i.e., a solvent, reductant, and protectant. Recent applications of DMF-stabilized metal NPs are summarized. These applications have enabled a versatile organic transformation such as cross-coupling reactions, hydrosilylation, and methylation to be achieved. These reactions proceed under low catalyst loadings and ligandless conditions., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

N , N -Dimethylformamide-stabilised Pd nanocluster (NC) catalysed cross-coupling reactions of hydrosilane/disilane have been investigated. In this reaction, the coupling reaction proceeds without ligands with low catalyst loading. N , N- Dimethylacetamide is a crucial solvent in these reactions. The solvent effect was considered by various techniques, such as transmission electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pd NCs can be recycled five times under both hydrosilane and disilane reaction conditions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

IrCl(cod) 2 ]/dppe-catalyzed α-methylation of aryl esters using methanol as the C1 source was developed. This methylation process is useful in several fields including organic chemistry, biochemistry, and medicinal chemistry. Readily available methanol as methylation reagent was successfully adapted. The reaction processed high atom economy and efficient. By applying the reaction system, the synthesis method of naproxen was provided.

An active in situ-generated Nb complex was used as a catalyst in the ring-closing metathesis reaction of N , N- diallyl- p -toluenesulfonamide to afford the corresponding 3-pyrroline derivative. The Nb complex was formed from NbCl 5 , trimethylsilyl chloride, Zn, and PhCHCl 2 in tetrahydrofuran. The Nb complex displayed high catalytic activity toward ring-closing metathesis reactions., Competing Interests: The authors declare no competing financial interest.

We show that N , N -dimethylformamide-stabilized Pd nanoclusters (NCs) have high catalytic activity in the reaction of substituted 2-iodoanilines with alkynes to give 2,3-disubstituted indoles. This indole synthesis does not require phosphine ligands and proceeds with low Pd catalyst loadings. The Pd NCs were separated from the mixture after the reaction, and recycled at least three times. Transmission electron microscopy images showed that the Pd particle size before the reaction was 1.5-2.5 nm. The particle size after the reaction was 2-3 nm. X-ray photoelectron spectroscopy showed that the binding energy of the Pd NCs before the reaction was 335.0 eV., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

NbCl 5 -catalyzed [2 + 2 + 2] cycloaddition of nitriles with alkynes was used to synthesize pyrimidine derivatives. In this reaction, the use of individual Lewis acids, namely NbCl 5 and FeCl 3 , is a key strategy for achieving the reaction using a catalytic amount of NbCl 5 . The roles of the two Lewis acids were investigated using FT-IR spectroscopy. The results showed that NbCl 5 served as an efficient Lewis acid catalyst for nitrile activation, whereas FeCl 3 showed stronger Lewis acidity toward pyrimidines, releasing NbCl 5 into the catalytic cycle.