CC Bond Formation <i>via</i> CH Activation and CN Bond Formation <i>via</i> Oxidative Amination Catalyzed by Palladium‐ Polyoxometalate Nanomaterials Using Dioxygen as the Terminal Oxidant

Chng, Leng Leng; Zhang, Jie; Yang, Jinhua; Amoura, Makhlouf; Ying, Jackie Y.

doi:10.1002/adsc.201100362

Cited by 63 publications

(36 citation statements)

References 89 publications

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“…Then, the oxidative dehydrogenation of the β‐aminoaldehyde takes place to give the corresponding enaminal (step 2 in Scheme ),6, 15 which is efficiently promoted by Au/OMS‐2. This mechanism is completely different from the traditional palladium‐catalyzed amination, which is supposed to proceed through migratory insertion of an amine into a palladium–alkene complex, followed by β‐hydride elimination 5e,g,h…”

Section: Methodsmentioning

confidence: 96%

“…In comparison with amidation, amination using simple amines as nucleophiles is a relatively less‐developed reaction,5, 6 likely because of the severe deactivation of homogeneous metal‐based catalysts by the strong coordination of amines. With regard to the amination of α,β‐unsaturated carbonyl compounds, the groups of Ishii5e,h and Ying5g have recently reported excellent palladium‐catalyzed procedures. However, α,β‐unsaturated carbonyl compounds suitable for these systems are limited to α,β‐unsaturated esters and ketones,7 and the scope of amines is also limited to only aniline derivatives 5e,g,h.…”

Section: Methodsmentioning

confidence: 99%

“…With regard to the amination of α,β‐unsaturated carbonyl compounds, the groups of Ishii5e,h and Ying5g have recently reported excellent palladium‐catalyzed procedures. However, α,β‐unsaturated carbonyl compounds suitable for these systems are limited to α,β‐unsaturated esters and ketones,7 and the scope of amines is also limited to only aniline derivatives 5e,g,h. Thus, the dehydrogenative amination of α,β‐unsaturated aldehydes to enaminals has never been previously reported.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Gold‐Catalyzed Heterogeneous Aerobic Dehydrogenative Amination of α,β‐Unsaturated Aldehydes to Enaminals

Jin¹,

Yamaguchi²,

Mizuno³

2013

Angewandte Chemie

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Although enaminals (β‐enaminals) are very important compounds and have been utilized as useful synthons for various important compounds, they have been synthesized through non‐green and/or limited procedures until now. Herein, we have successfully developed a green synthetic procedure using a heterogeneous catalyst. In the presence of gold nanoparticles supported on manganese‐oxide‐based octahedral molecular sieves OMS‐2 (Au/OMS‐2), dehydrogenative amination of α,β‐unsaturated aldehydes with amines proceeded efficiently, with the corresponding enaminals isolated in moderate to high yields (50–97 %). The catalysis was truly heterogeneous, and Au/OMS‐2 could be reused. Furthermore, the formal Wacker‐type oxidation of α,β‐unsaturated aldehydes to enaminones has been realized.

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Section: Methodsmentioning

confidence: 96%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Gold‐Catalyzed Heterogeneous Aerobic Dehydrogenative Amination of α,β‐Unsaturated Aldehydes to Enaminals

Jin¹,

Yamaguchi²,

Mizuno³

2013

Angewandte Chemie

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“…88 These materials were prepared by reduction of a Pd(NO 3 ) 2 salt with NaBH 4 in the presence of a carbon support and the appropriate POM, which also provides a suitable capping agent during the synthesis of the PdNPs, ensuring that they are uniform and well-dispersed with diameters of 2-3 nm (in contrast to particles formed in the absence of POM). 88 These materials were prepared by reduction of a Pd(NO 3 ) 2 salt with NaBH 4 in the presence of a carbon support and the appropriate POM, which also provides a suitable capping agent during the synthesis of the PdNPs, ensuring that they are uniform and well-dispersed with diameters of 2-3 nm (in contrast to particles formed in the absence of POM).…”

Section: Metal-metal Frameworkmentioning

confidence: 99%

Catalytic C–H bond functionalisation chemistry: the case for quasi-heterogeneous catalysis

2015

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This feature article examines the potential of heterogeneous Pd species to mediate catalytic C-H bond functionalisation processes employing suitable substrates (e.g. aromatic/heteroaromatic compounds). A focus is placed on the reactivity of supported and non-supported Pd nanoparticle (PdNPs) catalysts, in addition to the re-appropriation of well-established heterogeneous Pd catalysts such as Pd/C. Where possible, reasonable comparisons are made between PdNPs and traditional 'homogeneous' Pd precatalyst sources (which form PdNPs). The involvement of higher order Pd species in traditional cross-coupling processes, such as Mizoroki-Heck, Sonogashira and Suzuki-Miyaura reactions, allows the exemplification of potential future topics for study in the area of catalytic C-H bond functionalisation processes.

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“…IDO is an important new therapeutic target for the treatment of cancer. 52) Immobilized Pd NPs have been used effectively for the activation of C-H bonds. Although there have been several reports on the use of Pd-NPs as catalysts for activation of C(sp 2 )-H bonds, 53) there have been none describing the use of Pd-NPs for Pd-catalyzed activation of C-H bonds with the activation occurring via a key five-membered palladacycle intermediate.…”

Section: Introductionmentioning

confidence: 99%

Development of Metal Nanoparticle Catalysis toward Drug Discovery

Arisawa

2019

Chem. Pharm. Bull.

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Transition-metal nanoparticles (NPs) catalysts supported on solid material represent one of the most important subjects in organic synthesis due to their reliable carbon-carbon or carbon-heteroatom bondforming cross-coupling reactions. Therefore methodologically and conceptually novel immobilization methods for nonprecious transition-metal NPs are currently required for the development of organic, inorganic, green, materials, and medicinal chemistry. We discovered a self-assembled Au-supported Pd NPs catalyst (SAPd(0)) and applied it as a catalyst to Suzuki-Miyaura coupling, Buchwald-Hartwig reaction, Carbon(sp 2 and sp 3 )-Hydrogen bond functionalization, double carbonylation, removal of the allyl protecting groups of allyl esters, and redox switching. SAPd(0) comprises approximately 10 layers of self-assembled Pd(0) NPs, whose size is less than 5 nm on the surface of a sulfur-modified Au. The Pd NPs are wrapped in a sulfated p-xylene polymer matrix. We thought that the self-assembled Au-supported Pd NPs could be made by in situ metal NP and nanospace simultaneous organization (PSSO). This methodology involves 4 kinds of simultaneous procedures: i) reduction of a higher valence metal salt, ii) growth of metal NPs with appropriate size, iii) growth of a matrix with appropriate pores, and iv) wrapping of the metal NPs by matrix nanopores. This methodology is different from previously reported metal NPs-immobilizing methods, which use solid supports with preformed pores or coordination sites. We also applied the in situ PSSO method to prepare various immobilized transition-metal NPs, including base metals. For example, the in situ PSSO method can be applicable to easily prepare Ni, Ru, and Fe NPs with good recyclability and low metal leaching for use in organic synthesis. . His current research interest is in organic chemistry toward the development of medicinal chemistry. 735 Chem. Pharm. Bull. indicate that the sulfur on Au was reduced and had chemically bonded with Pd during Pd adsorption. In Pd 2p core-level photoemission spectra, the peaks from A appear close to the metallic Pd peak. These results suggest that, in the case of A, Pd(dba) 2 molecules were changed to zerovalent molecules or metallic Pd, as summarized in Fig. 4.Single crystal Au(111)/mica is not versatile. Eventually, instead of Au(111)/mica, we used Au foil and mesh to prepare B and C according to the Pd-adsorption procedure for A. When A, B, or C was subjected to the Suzuki-Miyaura coupling of 1a and 2a, the yields of the product 3a for runs 1 to 10 were excellent to quantitative in all cases, as shown in Table 1, entries 1-3. Entry 4 indicates that Material D, which was prepared from Au(mesh) with Pd(OAc) 2 as a Pd-source, was also highly active for the Suzuki-Miyaura coupling. These results show that the Pd materials A, B, C, and D are highly reactive and recyclable in this reaction.Next, we measured the amount of Pd on the Pd materials B-D using inductively coupled plasma mass spectrometry (ICP-MS) analysis. These analyses showed that in ...

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CC Bond Formation via CH Activation and CN Bond Formation via Oxidative Amination Catalyzed by Palladium‐ Polyoxometalate Nanomaterials Using Dioxygen as the Terminal Oxidant

Cited by 63 publications

References 89 publications

Gold‐Catalyzed Heterogeneous Aerobic Dehydrogenative Amination of α,β‐Unsaturated Aldehydes to Enaminals

Gold‐Catalyzed Heterogeneous Aerobic Dehydrogenative Amination of α,β‐Unsaturated Aldehydes to Enaminals

Catalytic C–H bond functionalisation chemistry: the case for quasi-heterogeneous catalysis

Development of Metal Nanoparticle Catalysis toward Drug Discovery

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