Carboxylate Salt Bridge‐Mediated Enamine Catalysis: Expanded Michael Reaction Substrate Scope and Facile Access to Antidepressant (<i>R</i>)‐Pristiq

Nugent, Thomas C.; Hussein, Hussein Ali El Damrany; Ahmed, Sajjad; Najafian, Foad Tehrani; Hussain, Ishtiaq; Georgiev, Tony; Al-Joumhawy, Mahmoud

doi:10.1002/adsc.201700801

Cited by 11 publications

(7 citation statements)

References 50 publications

(28 reference statements)

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“…Finally, Nugent et al elaborated a fundamentally new approach to the synthesis of enantiomerically pure desvenlafaxine based on Michael addition, followed by the reduction of the nitro group and reductive methylation (Scheme 36). 92 At the methylation step (conversion of 2.12.2.h in 2.12.2), 10 equiv of formaldehyde was used to achieve an isolated yield of 80% (240 mg of the product, 33% RME).…”

Section: Desvenlafaxine and Venlafaxinementioning

confidence: 99%

Reductive Amination in the Synthesis of Pharmaceuticals

et al. 2019

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Reductive amination plays a paramount role in pharmaceutical and medicinal chemistry owing to its synthetic merits and the ubiquitous presence of amines among biologically active compounds. It is one of the key approaches to C–N bond construction due to its operational easiness and a wide toolbox of protocols. Recent studies show that at least a quarter of C–N bond-forming reactions in the pharmaceutical industry are performed via reductive amination. This Review concisely compiles information on 71 medical substances that are synthesized by reductive amination. Compounds are grouped according to the principle of action, which includes drugs affecting the central nervous system, drugs affecting the cardiovascular system, anticancer drugs, antibiotics, antiviral and antifungal medicines, drugs affecting the urinary system, drugs affecting the respiratory system, antidiabetic medications, drugs affecting the gastrointestinal tract, and drugs regulating metabolic processes. A general synthetic scheme is provided for each compound, and the description is focused on reductive amination steps. The green chemistry metric of reaction mass efficiency was calculated for all reactions.

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Section: Desvenlafaxine and Venlafaxinementioning

confidence: 99%

Reductive Amination in the Synthesis of Pharmaceuticals

et al. 2019

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“…From this point of view, a number of hitherto known heterogeneous catalysts, such as Pd/C, 3 Pd/CaCO 3 , 4 PtO 2 , 5 and Raney Ni, 6 were employed with H 2 gas for the synthesis of drug compounds. Kobayashi and co-workers reported the application of the Pt/C catalyst system in a column-type reactor for the continuous flow synthesis of Donepezil and Arfomoterol/Tamsulosin precursors.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Reductive Alkylation of Amines in Batch and Microflow Conditions Using a Silicon-Wafer-Based Palladium Nanocatalyst

2020

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We describe the development of the catalytic reductive alkylation of amines with aldehydes under the atmospheric pressure of H 2 using a brush-like silicon-nanostructure-supported palladium nanoparticle composite (SiNS–Pd) as a silicon-wafer-based reusable heterogeneous catalyst. The present reaction of primary and secondary amines with various aliphatic and aromatic aldehydes in the presence of the catalyst (0.02–0.05 mol % Pd) gave the corresponding secondary and tertiary amines including Lomerizine and Aticaprant in a 68% quantitative yield without overalkylation. We also designed and fabricated a flow device equipped with SiNS–Pd for microflow reactions, which was applied to the gas–liquid–solid triphasic reaction system (i.e., H 2 gas, a substrate solution, and a solid catalyst). A multigram-scale reaction of aniline and benzaldehyde was demonstrated to obtain N -benzylaniline (ca. 4 g/day), in which the internal volume of the flow channel was 43 μL, the residence time was approximately 1 s, and the turnover number (TON) reached 4.0 × 10 4 in a continuous 24 h run (1.7 × 10 3 h –1 ; 0.50 s –1 ).

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“…Only when the two hydroxyl groups are adjacent to each other is it possible to form a five-membered cyclic boronate, which could explain the lower yield of 1p . It is worthy to note that the nitro alkenes with hydroxyls and an amino group ( 1o , 1p , and 1s ) were commonly prepared in an acetic acid-ammonium acetate mixture under reflux in the literature, − whereas in this fiber-catalyzed synthesis, mild reaction conditions were used without employing acetic acid as an irritative solvent. Moreover, electron-rich heterocyclic aldehydes afforded the corresponding products such as 1t and 1u satisfactorily.…”

Section: Resultsmentioning

confidence: 99%

Cooperative Catalysis by Boronic Acid-Amine Bifunctionalized Polyacrylonitrile Fibers in Henry Reaction

Zhang

et al. 2023

ACS Catal.

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The acid–base pairing and fabrication method was herein employed to construct acid–base bifunctional heterogeneous catalysts. The boronic acid group was introduced into primary amine-functionalized polyacrylonitrile fiber (PANEAF) via amide bond formation to fabricate boronic acid-amine bifunctional PANFs as recyclable heterogeneous catalysts by using the amino N atoms of PANEAF as anchoring points. The so-obtained fiber catalysts PANEA–BA1F and PANEA–BA2F containing boronic acid groups attached on benzene and pyridine rings, respectively, were employed in the Henry reactions of aryl aldehydes with nitromethane. Catalytic investigations showed that their performance had great correlation with the change of boronic acid. PANEA–BA2F exhibited a higher substrate selectivity than PANEA–BA1F, and only the benzaldehydes with hydroxy, dimethylamino, and amide groups were reactive, which showed preliminary substrate specificity like enzyme catalysis. The in situ investigation with cyclododecane as solvent by Raman and Fourier transform infrared spectroscopy (FT-IR) analysis was conducted to clarify the catalytic difference. Moreover, the uncommon reverse reactivity order of benzaldehydes in PANEA–BA1F-catalyzed condensation was explained.

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Carboxylate Salt Bridge‐Mediated Enamine Catalysis: Expanded Michael Reaction Substrate Scope and Facile Access to Antidepressant (R)‐Pristiq

Cited by 11 publications

References 50 publications

Reductive Amination in the Synthesis of Pharmaceuticals

Reductive Amination in the Synthesis of Pharmaceuticals

Catalytic Reductive Alkylation of Amines in Batch and Microflow Conditions Using a Silicon-Wafer-Based Palladium Nanocatalyst

Cooperative Catalysis by Boronic Acid-Amine Bifunctionalized Polyacrylonitrile Fibers in Henry Reaction

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