Organic reaction in water. Part 3: A facile method for reduction of aromatic rings using a raney Ni–Al alloy in dilute aqueous alkaline solution under mild conditions

Tsukinoki, Takehito; Kanda, Tadashige; Liu, Guobin; Tsuzuki, Hirohisa; Tashiro, Masashi

doi:10.1016/s0040-4039(00)00636-5

Cited by 37 publications

(11 citation statements)

References 16 publications

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“…Preparation according to general procedure 1 using rac-3 (crude product) yielded rac-4 (72.6 mg, 0.31 mmol, 11%) as a colorless solid. 1 [17,18], thiazolidine (S)-2 (92.6 mg, 0.58 mmol) was dissolved in H 2 O (10 mL), methanol (2% v/v) and Ni/Al alloy (1.06 g; 50 wt% Ni, 50 wt% Al) are added. The mixture was heated to 90 • C and 1% aqueous (aq.)…”

Section: General Procedures 1 For Derivatization Using Phenylisocyanatementioning

confidence: 99%

“…Therefore, we first conducted a screening of different methodologies which we considered to be suitable for the desired reductive desulfurization of this 3-thiazolidine (S)-2 using the racemic secondary amine rac-3, which was previously prepared, as a reference. The first method, which we applied in our experiments, was based on utilizing a Ni/Al-based alloy as a reducing agent following a protocol reported by Whitman et al and Tsukinoki et al (Scheme 3) [17,18]. Accordingly, a solution of (S)-2 in distilled water and methanol was treated with this Ni/Al-reducing agent, followed by adding a solution of KOH after increasing the temperature of this suspension to 90 • C. However, in these experiments, we did not observe any formation of the desired amine (S)-3.…”

Section: Reductive Desulfurization Of Thiazolidine (S)-2mentioning

confidence: 99%

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Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

et al. 2019

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A proof of concept for a novel approach towards enantiomerically highly enriched acyclic secondary amines and β-aminothiols as non-cyclic target molecules when starting from 3-thiazolines as heterocycles is presented. Starting from 2,2,4,5,5-pentamethyl-3-thiazoline, we demonstrated this chemoenzymatic pathway to both of these types of amine molecules, which were isolated as urea derivatives with a non-optimized yield of up to 20%. As a substrate, 2,2,4,5,5-pentamethyl-3-thiazolidine, which was obtained with an enantiomeric excess (ee) of 99% in a biotransformation from the corresponding 3-thiazoline according to a recently developed protocol, was used. For the reductive desulfurization of this substrate leading to a sulfur-free secondary amine, in situ formed Ni2B turned out to be a suitable reducing reagent. However, when using lithium aluminum hydride as a reducing agent, β-aminothiol was obtained.

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Section: General Procedures 1 For Derivatization Using Phenylisocyanatementioning

confidence: 99%

Section: Reductive Desulfurization Of Thiazolidine (S)-2mentioning

confidence: 99%

Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

et al. 2019

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“…In order to develop the catalyst with high BP conversion and CBH selectivity in the selective hydrogenation reaction of BP, many researchers have made extensive efforts. Tsukinoki et al [13] . found that the CHB selectivity over Raney Ni−Al alloy in dilute aqueous alkaline solution without any organic solvents at 90 °C under atmospheric pressure could reach to 95 %.…”

Section: Introductionmentioning

confidence: 99%

Effects of Ni‐Loading on the Performance of Ni/SiO₂ Catalysts for the Highly Selective Hydrogenation of Biphenyl to Cyclohexylbenzene

Zhao

et al. 2021

ChemistrySelect

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This article investigated the effects of Ni loading on the performance of Ni/SiO2 catalysts for the selective hydrogenation of biphenyl (BP) to cyclohexylbenzene (CHB). The catalysts were characterized by the techniques of thermogravimetric analysis, X‐ray powder diffraction, N2‐physisorption, scanning electron microscope, inductively coupled plasma‐atomic emission spectroscopy, transmission electron microscope, H2 temperature‐programmed reduction. It was found that under the given reaction conditions, BP conversion showed an increased trend with the increasing Ni loading. However, 25 % Ni/SiO2 catalyst exhibited the lower CHB yield than 20 % Ni/SiO2 catalyst, which was attributed to the overhydrogenation of BP on the former with the excessive metal active sites. Besides, over 25 % Ni/SiO2 catalyst, BP conversion gradually increased with the extended reaction time, the enhanced hydrogen pressure or the improved temperature, but CHB selectivity and yield increased first and then decreased. Additionally, isopropanol was considered to be the best one among the representative solvents in BP hydrogenation reaction. Moreover, the conversion of BP and the selectivity/yield of CHB could keep above 99 % and 96 %, respectively, after eight consecutive cycles.

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“…In the absence of any organic solvents under milder reaction conditions, dilute sodium or potassium hydroxide solutions were applied to accelerate the reduction systems. [33][34][35][36] Recently, reduction or the oxido-reduction reaction of cinnamaldehyde and its derivatives with Ni-Al alloy and Al powder in water was also reported. 37 The utilization of water as a chemical reagent is an essential aspect of Green Chemistry.…”

Section: Introductionmentioning

confidence: 99%

Reduction of phenylacetylenes using Raney Ni–Al alloy, Al powder in the presence of noble metal catalysts in water

Yamato¹,

Rayhan²,

Kowser³

et al. 2017

Arkivoc

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The chemoselective reduction is based on the reaction between Al either as powder or from the alloy and water which generates in situ hydrogen to effect the reduction of the targeted functional groups. Raney Ni-Al alloy with Al powder can reduce phenylacetylenes to the corresponding ethylbenzene (3) in water in excellent yield at 120 °C for 6 h in a sealed tube. In addition, the complete reduction of the aromatic ring to ethylcyclohexane required 60 o C for 12 h with Raney Ni-Al alloy, Al powder in the presence of Pt/C. Appropriate selection of reaction conditions allowed the selective preparation of ethylbenzene as well as ethylcyclohexane from phenylacetylene.

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Organic reaction in water. Part 3: A facile method for reduction of aromatic rings using a raney Ni–Al alloy in dilute aqueous alkaline solution under mild conditions

Cited by 37 publications

References 16 publications

Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

Effects of Ni‐Loading on the Performance of Ni/SiO₂ Catalysts for the Highly Selective Hydrogenation of Biphenyl to Cyclohexylbenzene

Reduction of phenylacetylenes using Raney Ni–Al alloy, Al powder in the presence of noble metal catalysts in water

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Organic reaction in water. Part 3: A facile method for reduction of aromatic rings using a raney Ni–Al alloy in dilute aqueous alkaline solution under mild conditions

Cited by 37 publications

References 16 publications

Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines

Effects of Ni‐Loading on the Performance of Ni/SiO2 Catalysts for the Highly Selective Hydrogenation of Biphenyl to Cyclohexylbenzene

Reduction of phenylacetylenes using Raney Ni–Al alloy, Al powder in the presence of noble metal catalysts in water

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Effects of Ni‐Loading on the Performance of Ni/SiO₂ Catalysts for the Highly Selective Hydrogenation of Biphenyl to Cyclohexylbenzene