Transformation of 2-(Hydroxymethyl)-5-(aminomethyl)-furan into 6-Methyl-3-pyridinol.

Elming, Niels; Clauson-Kaas, Niels; Anderson, E. P.; Eliasson, N. A.; Thorell, B.

doi:10.3891/acta.chem.scand.10-1603

Cited by 32 publications

(9 citation statements)

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“…The period of reaction was usually about 1 h. However, furfural was completely transformed to furan-2-ylmethanmine after 10 min under the reaction conditions given, while benzophenone was heated for 3.5 h. One year later, Wayne and Adkins presented the reaction of d-glucose in a methanol−NH 3 solution over Raney Ni at 100−115 °C and 152 bar H 2 within less than 1 h (Scheme 29C). 67 A mixture of products resulted, from which d-glucamine was separated in a yield of 26% as the benzal 75 I, a pale yellow liquid and a new compound at the time, was prepared in a multigram scale (9.30 g) in a yield of 72%. In the same year, Surrey and Lesher described the synthesis of 2,4-dichlorophenethylamine and 4butoxybenzylamine by reductive amination of 2,4-dichlorophenylacetonitrile and 4-butoxybenzaldehyde in methanolic NH 3 at 69 bar H 2 pressure (Scheme 34B).…”

Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 99%

“…Results of the reductive amination with liquid NH 3 using Raney Ni as a catalyst from the years 1956 to 1968 are summarized in Scheme . The transformation of 5-(hydroxymethyl)-furfural into 2-(hydroxymethyl)-5-(aminomethyl)-furan I (Scheme A) was introduced by Elming and Clauson-Kaas in 1956 …”

Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 99%

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Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

2020

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The reductive amination, the reaction of an aldehyde or a ketone with ammonia or an amine in the presence of a reducing agent and often a catalyst, is an important amine synthesis and has been intensively investigated in academia and industry for a century. Besides aldehydes, ketones, or amines, starting materials have been used that can be converted into an aldehyde or ketone (for instance, carboxylic acids or organic carbonate or nitriles) or into an amine (for instance, a nitro compound) in the presence of the same reducing agent and catalyst. Mechanistically, the reaction starts with a condensation step during which the carbonyl compound reacts with ammonia or an amine, forming the corresponding imine followed by the reduction of the imine to the alkyl amine product. Many of these reduction steps require the presence of a catalyst to activate the reducing agent. The reductive amination is impressive with regard to the product scope since primary, secondary, and tertiary alkyl amines are accessible and hydrogen is the most attractive reducing agent, especially if large-scale product formation is an issue, since hydrogen is inexpensive and abundantly available. Alkyl amines are intensively produced and use fine and bulk chemicals. They are key functional groups in many pharmaceuticals, agro chemicals, or materials. In this review, we summarize the work published on reductive amination employing hydrogen as the reducing agent. No comprehensive review focusing on this subject has been published since 1948, albeit many interesting summaries dealing with one or the other aspect of reductive amination have appeared. Impressive progress in using catalysts based on earth-abundant metals, especially nanostructured heterogeneous catalysts, has been made during the early development of the field and in recent years.

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Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 99%

Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 99%

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

2020

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“…It can be utilized to synthesize a number of nitrogenous furan chemicals including pharmaceuticals and polymers . It also can be utilized to produce pyridine compounds, such as 5‐hydroxy‐2‐pyridinemethanol, and 6‐methyl‐3‐pyridinol through a simple hydrolysis process. This compound is generally produced from furfural; however, preparation procedures usually include long reaction times and multi‐reaction steps.…”

Section: Introductionmentioning

confidence: 99%

Preparation of 5‐(Aminomethyl)‐2‐furanmethanol by direct reductive amination of 5‐Hydroxymethylfurfural with aqueous ammonia over the Ni/SBA‐15 catalyst

Chen

Sun

et al. 2018

J of Chemical Tech & Biotech

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BACKGROUND 5‐(Aminomethyl)‐2‐furanmethanol (AMF), used widely in medicinal chemistry, is usually synthesized by the reductive amination of furfural or 5‐hydroxymethylfurfural (HMF) with ammonia. However, a challenging task when synthesizing this furyl primary amine is to enhance the selectivity of the product due to its high nucleophilicity. Conventional measures have used excessive liquid ammonia and precious metal catalysts. Usually, the molar ratio of ammonia to substrate is up to 30:1. This study employed aqueous ammonia to synthesize AMF by the direct reductive amination of HMF using the non‐noble metal Ni/SBA‐15 catalyst. RESULTS The Ni/SBA‐15 catalyst displayed higher catalytic selectivity in the reductive amination of HMF to AMF compared to other precious metal catalysts, such as Ru/C, Pd/C and Pt/C. The AMF yield of 89.8% was obtained at the relatively mild reaction temperature of 100 °C for 4 h. After the fifth cycle, an acceptable decrease in catalytic activity with 74.2% yield of AMF was observed. CONCLUSION An improved process was developed for preparing AMF by the reductive amination of HMF with aqueous ammonia using the non‐noble Ni/SBA‐15 catalyst. The high selectivity of nickel catalyst is attributed mainly to the moderate catalytic activity. Moreover, a small amount of water enhanced the yield of AMF by promoting the formation of ammonium ions to prevent the further side reaction of AMF with HMF. Results of recycling experiments and analyses showed that agglomeration, loss and oxidization of nickel species together with carbon deposition were responsible for the slight deactivation of the catalyst. © 2018 Society of Chemical Industry

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“…208 In related ways, 2-(hydroxymethyl)-5-(aminomethyl)-furan 75 can be converted to 6-methyl-3-pyridinol 78 with a high yield of 88% via cascade hydrolysis and cyclization catalyzed by HCl under reflux (Scheme 21C). 209…”

Section: Green Chemistry Critical Reviewmentioning

confidence: 99%