Continuous flow ring-closing metathesis, an environmentally-friendly route to 2,5-dihydro-1H-pyrrole-3-carboxylates

Drop, Marcin; Bantreil, Xavier; Grychowska, Katarzyna; Mahoro, Gilbert Umuhire; Colacino, Evelina; Pawłowski, Maciej; Martinez, Jean; Subra, Gilles; Zajdel, Paweł

doi:10.1039/c7gc00235a

Cited by 23 publications

(12 citation statements)

References 72 publications

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“…Similar improvements were obtained when RCM was employed for the formation of smaller rings [601]. isolated in moderate to high yields (Scheme 164) [602]. The system allowed the larger scale processing of 687 (10 g) and after 37 minutes the product 689 was isolated in 91% yield, with comparable result as obtained on a 1 mmol scale in batch.…”

Section: Metathesissupporting

confidence: 60%

“…Lamaty et al described a continuous-flow setup where a reaction in dimethyl carbonate (DMC) was passed into the coil at 110–120 °C for 1–5 minutes and 2,5-dihydro-1 H -pyrroles were isolated in moderate to high yields ( Scheme 164 ) [ 602 ]. The system allowed the larger scale processing of 687 (10 g) and after 37 minutes the product 689 was isolated in 91% yield, with comparable result as obtained on a 1 mmol scale in batch.…”

Section: Reviewmentioning

confidence: 99%

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A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

Gambacorta¹,

Sharley²,

Baxendale³

2021

Beilstein J. Org. Chem.

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Due to their intrinsic physical properties, which includes being able to perform as volatile liquids at room and biological temperatures, fragrance ingredients/intermediates make ideal candidates for continuous-flow manufacturing. This review highlights the potential crossover between a multibillion dollar industry and the flourishing sub-field of flow chemistry evolving within the discipline of organic synthesis. This is illustrated through selected examples of industrially important transformations specific to the fragrances and flavours industry and by highlighting the advantages of conducting these transformations by using a flow approach. This review is designed to be a compendium of techniques and apparatus already published in the chemical and engineering literature which would constitute a known solution or inspiration for commonly encountered procedures in the manufacture of fragrance and flavour chemicals.

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Section: Metathesissupporting

confidence: 60%

Section: Reviewmentioning

confidence: 99%

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

Gambacorta¹,

Sharley²,

Baxendale³

2021

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

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“…ChemSusChem 2018, 11,3157 -3166 www.chemsuschem.org green solvent, [61,62] but unfortunately,w as rather seldom used in the context of RCM. [56,63] The first experiment in EtOAc was performed at 1.5 mm concentration in the presence of 2mol %c atalyst and led to a 91 %y ield of 26 (Table 3, entry 1)-the result was almostt he same as the one obtained in toluene (Table 2, entry 10). Subsequent experiments were conducted at increasingly higher substrate concentrations and at lower catalyst loading.…”

Section: Scope and Limitation Studymentioning

confidence: 71%

Preparation of Musk‐Smelling Macrocyclic Lactones from Biomass: Looking for the Optimal Substrate Combination

et al. 2018

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Macrocyclic musk belongs to a well-known and valued class of the fragrance family. Originally, natural musks were obtained from rectal musk glands which often led to the death of the animals. Recently, a lot of effort was invested to obtain such macrocycles in a synthetic way. This research presents a study on the preparation of macrocyclic lactones with the musk scent by ring-closing metathesis (RCM) using biomass-derived starting materials: oleic and 9-decenoic acid. An experimental rule correlating the C-C double bond substitution pattern in the starting diene and the yield for the RCM macrocyclization was proposed.

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“…reported a synthetic flow approach for the synthesis of 2,5‐dihydropyrrole‐3‐carboxylates in high yields, with low residence times and good scale‐up ability, through ruthenium‐catalyzed ring‐closing metathesis of diallylamines, in dimethyl carbonate (Scheme ). Lower yields were obtained for derivatives bearing a methoxy group at meta position or a chloride at para position of the aryl substituents …”

Section: Heterocyclic Synthesismentioning

confidence: 99%

Flow Chemistry: Towards A More Sustainable Heterocyclic Synthesis

2019

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Flow Chemistry is a revolutionary field in Organic Chemistry. By changing the conventional methods and apparatus applied in the chemical synthesis, flow chemistry emerges as a game changer for organic synthesis laboratories, in both academia and industries. Considered as a sustainable practice, flow processes play an important role in the development of fine chemical products and in drug discovery development pro- [a] The main advantages of flow chemistry are that it allows the reaction to be carried out safely with high selectivity, high reproducibility and reduced energy consumption/carbon footprint. These features make this emerging technology for organic synthesis desirable for green and sustainable chemical synthesis, giving the chemist time for work planning and design, instead of using it in repetitive tasks, [5b,12] as expressed by the CHEM21 project by awarding a green flag for continuousflow reactions, in opposition to an amber flag for those performed under batch conditions. [13] Pedro Brandão received his MSc in Pharmaceutical Sciences from the Faculty of Pharmacy -University of Porto, in 2011. Pursuing his passion on studies in the field of Drug Discovery and Development, he is currently undergoing his PhD studies in Chemistry, in the field of Catalysis and Sustainability. His main focus of work is the discovery of new drug candidates through sustainable techniques. Marta Pineiro received her Ph.D. in Organic Chemistry in 2003 in the University of Coimbra, Portugal, and since 2002 has been enrolled at the University of Coimbra, being at present Auxiliary Professor. Her research interests are in the area of sustainable organic synthesis, microwave-assisted organic synthesis and synthesis and biological applications of tetrapyrrolic macrocycles. Teresa M. V. D. Pinho e Melo studied Chemistry at the University of Coimbra, where she graduated in 1985, got her M. 7191CPBA) as the oxidizing agent, avoiding the handling of this expensive and explosive reagent. [25] Recently, Morodo et al. explored the synthesis of two very important oxiranes (epichlorohydrin and glycidol) from biobased glycerol, under flow conditions. As depicted in Scheme 1, and using pimelic acid as the catalyst (10 mol-%), a sequential hydrochlorination/dichlorination process allows high conversion of glycerol (> 99 %) into 1,3-dichloro-2-propanol, followed by the quantitative conversion into a separable mixture of glycidol and epichlorohydrin (2:3). The separation of these two products is performed by an in-line membrane separation system, which allows the first product to be collected in the aqueous phase, while the second is collected in MTBE. This heterocycle can be further used as a synthetic precursor to relevant APIs bearing -amino alcohol moieties (e.g., propranolol, alprenolol and naftopidil). [26] Scheme 1. Sequential flow setup for the preparation of glycidol and epichlorohydrin, important APIs synthetic intermediates.Scheme 3. Synthesis and inline purification of a bicyclic aziridine (SGMR = silicon-glass microfluidic react...

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Continuous flow ring-closing metathesis, an environmentally-friendly route to 2,5-dihydro-1H-pyrrole-3-carboxylates

Abstract: Ring-closing metathesis, realized in continuous flow using dimethyl carbonate as a solvent, allowed us to convert up to 10 g of dienes into important building blocks.

Cited by 23 publications

References 72 publications

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

Preparation of Musk‐Smelling Macrocyclic Lactones from Biomass: Looking for the Optimal Substrate Combination

Flow Chemistry: Towards A More Sustainable Heterocyclic Synthesis

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