ChemInform Abstract: Manganese Dioxide Catalyzed N‐Alkylation of Sulfonamides and Amines with Alcohols under Air.

Yu, Xiaochun; Liu, Chuanzhi; Jiang, Lan; Xu, Qing

doi:10.1002/chin.201213049

Cited by 4 publications

(5 citation statements)

References 1 publication

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“…The most significant difference between these two catalysts is the conversion difference between 1a and 2a, which can reflect that these two catalysts mediated the present α-alkylation of ketones with alcohols via a different mechanism. In addition, MnO 2 has been reported to mediate alcohol transformations through an oxidation and MPV reduction sequence (Scheme 1b), 27,28 and other simple Mn oxides (Mn 2 O 3 , Mn 3 O 4 , and MnO) gave benzaldehyde (6a) and/or intermediate 4aa.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Heterogeneous Low-Valent Mn Catalysts for α-Alkylation of Ketones with Alcohols through Borrowing Hydrogen Methodology

et al. 2022

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Alcohol transformations through the borrowing hydrogen (BH) methodology have attracted attention due to its high atom economy and substrate availability. Nonprecious metal heterogeneous catalysts have recently been extensively explored; however, the difficulty in the observation of the active metal species has prevented mechanistic studies. Here, we report on supported Mn catalysts that act as reusable heterogeneous catalysts for the construction of C–C bonds by the α-alkylation of ketones with alcohols through the BH methodology. The catalyst, a Mn2+ species-MgO mixture-deposited Al2O3 support (Mn-MgO/Al2O3), exhibits catalytic performance for the reactions to give the corresponding products in 50–92% yield. The present catalyst did not require the addition of homogeneous strong bases that are typically indispensable for these reactions using the reported Mn-based heterogeneous catalysts and that require large energy consumption for separation, recycling, and waste treatment. While the addition of bases to such reaction systems has been considered to accelerate the dehydrogenation of alcohols and/or aldol condensation, MgO in Mn-MgO/Al2O3, a heterogeneous base, does not contribute to these steps. Fourier transform infrared spectroscopy (FT-IR) measurements indicated not only the incorporation of Mn hydride species, which has never been observed on heterogeneous Mn-based catalysts by the dehydrogenation of alcohols, but also enhancement of the hydrogenating capability of the Mn hydride species by co-deposited MgO on Al2O3. While such hydride species had been found to accelerate direct amination of alcohols over a metallic Ru nano particles-MgO mixture, the present study reveals that the reaction mechanism is extended to α-alkylation of ketones with alcohols over oxidized Mn, a base metal, in contact with MgO.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Heterogeneous Low-Valent Mn Catalysts for α-Alkylation of Ketones with Alcohols through Borrowing Hydrogen Methodology

et al. 2022

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“…The best performance was observed with CuNiAlO x as catalyst among all the samples attempted (entries 5, 7−9). Noteworthy, the choice of bases was crucial for this reaction as the base is an important cocatalyst to promote the alcohol activation to generate the ketone/aldehyde intermediate in "hydrogen transfer reaction" 23,33 (Table S2, entries 1−6). Solvents also play important roles, and it seems that solvents with high boiling point and low polarity may lead to high conversion and selectivity (entries 7− 12).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Sustainable Catalytic Amination of Diols: From Cycloamination to Monoamination

Yuan

Shi

2017

ACS Sustainable Chem. Eng.

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N-Alkyl amines are extensively applied in the synthesis of functional materials, pharmaceuticals, and pesticides. The reaction of diols with amines is attractive and has been investigated for more than 30 years by using iridium, ruthenium, and other catalysts. However, the main products with diols as starting materials, especially for C 4 −C 6 diols, are N-heterocyclic compounds because cyclization reaction is favorable in thermodynamics. Here, for the first time, a simple and non-noble catalyst CuNiAlO x prepared by a coprecipitation method was developed for the reaction of C 4 −C 6 diols with amines to give monoamination products. This method offers an efficient and environmentally friendly method for the selective monoamination of diols.

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“…Apart from the noble metals, non-noble-metal catalysts, such as Fe [123], Cu [124,125], Ni [19], Mn [126] and zeolite [127] are also demonstrated for this same reaction. These catalysts generally suffer from low catalytic activity, limited substrate scope, or harsh reaction conditions, i.e., the need for elevated temperatures under an H 2 atmosphere or a large amount of basic co-catalyst as additives.…”

Section: N-alkylation Of Amines With Alcoholsmentioning

confidence: 90%

Green Chemical Synthesis in the Presence of Nanoparticles as Catalysts

Touchy

2023

Emerging Applications of Nanomaterials

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As part of the heterogeneous catalysis concept, nanoparticle catalysis is the advanced key technology to connect the divergence between classical chemical synthesis methods and environmentally benign sustainable synthesis processes. The demonstration of nanoparticle catalysts for the sustainable and mild synthesis of chemicals is a fast-growing area in catalysis. This chapter will focus on a series of catalytic systems for hydrogen transfer-type or so-called borrowing hydrogen reactions using supported metal catalysts to synthesize chemicals directly and will highlight a group of coupling reactions that generates C-O, C-C, C-N, and C-S bonds. These catalytic coupling reactions possess a general mechanistic aspect: dehydrogenation of poor electrophile alcohols/amines to activated electrophiles, condensation (self or cross or with different nucleophiles), and hydrogenation of condensate. The feasibility of these catalytic coupling reactions is abided with the proper catalyst design where supports are enriched with acidic, basic, or amphoteric properties that promote the condensation reactions, and metal nanoparticle sites are responsible for the hydrogen transfer from the alcohols or amines followed by the re-hydrogenation of the condensation product accordingly. Compared to the state-of-the-art homogeneous catalytic systems, these heterogeneous metal nanoparticle-catalyzed reactions possess catalytic reusability, catalytic efficiency, and sustainability advantages.

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ChemInform Abstract: Manganese Dioxide Catalyzed N‐Alkylation of Sulfonamides and Amines with Alcohols under Air.

Cited by 4 publications

References 1 publication

Heterogeneous Low-Valent Mn Catalysts for α-Alkylation of Ketones with Alcohols through Borrowing Hydrogen Methodology

Heterogeneous Low-Valent Mn Catalysts for α-Alkylation of Ketones with Alcohols through Borrowing Hydrogen Methodology

Sustainable Catalytic Amination of Diols: From Cycloamination to Monoamination

Green Chemical Synthesis in the Presence of Nanoparticles as Catalysts

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