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

Sytniczuk, Adrian; Leszczyńska, Agnieszka; Kajetanowicz, Anna; Grela, Karol

doi:10.1002/cssc.201801463

Cited by 31 publications

(32 citation statements)

References 79 publications

(129 reference statements)

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“…Green chemistry is an increasing trend not only in chemical industry but also in academia. 59 − 62 Despite the environmental needs and the availability of many alternative solvents such as water, 63 ethyl acetate, 64 , 65 dimethyl carbonate, 66 , 67 2-MeTHF, 68 , 69 and 4-MeTHP, 61 , 70 the usage of green solvent for olefin metathesis is relatively scarce. We therefore screened both the general-purpose Hoveyda–Grubbs second-generation catalyst ( Ru1 , see Figure 1 ) and the tagged StickyCat PF 6 ( Ru2 ) in RCM of diethyl diallylmalonate ( 1 ) used as a model substrate, in two solvent systems—DCM (not green) and EtOAc (green).…”

Section: Results and Discussionmentioning

confidence: 99%

Olefin Metathesis in Continuous Flow Reactor Employing Polar Ruthenium Catalyst and Soluble Metal Scavenger for Instant Purification of Products of Pharmaceutical Interest

Toh

Patrzałek

Nienałtowski

et al. 2021

ACS Sustainable Chem. Eng.

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In recent years, the development of continuous-flow reactors has attracted growing attention from the synthetic community. Moreover, findings in the precise control of the reaction parameters and improved mass/heat transfer have made the flow setup an attractive alternative to batch reactors, both in academia and industry, enabling safe and easy scaling-up of synthetic processes. Even though a majority of the pharmaceutical industry currently rely on batch reactors or semibatch reactors, many are integrating flow technology because of easier maintenance and lower risks. Herein, we demonstrate an operationally simple flow setup for homogeneous ring-closing metathesis, which is applicable to the synthesis of active pharmaceutical ingredients precursors or analogues with high efficiency, low residence time, and in a green solvent. Furthermore, through the addition of a soluble metal scavenger in the subsequent step within the flow system, the level of ruthenium contamination in the final product can be greatly reduced (to less than 5 ppm). To ensure that this method is applicable for industrial usage, an upscale process including a 24 h continuous-flow reaction for more than 60 g of a Sildenafil analogue was achieved in a continuous-flow fashion by adjusting the tubing size and flow rate accordingly.

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Section: Results and Discussionmentioning

confidence: 99%

Olefin Metathesis in Continuous Flow Reactor Employing Polar Ruthenium Catalyst and Soluble Metal Scavenger for Instant Purification of Products of Pharmaceutical Interest

Toh

Patrzałek

Nienałtowski

et al. 2021

ACS Sustainable Chem. Eng.

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“…At the end of the twentieth century, only a few reported syntheses employing OM were known [588][589][590], often due to issues with selectivity and poor activity of the catalysts. Later, with progress in the catalyst design (especially stabilising ligand framework), various multistep preparations of macrocycles were being described [591][592][593][594][595][596][597][598][599]. However, common to all these examples is that ring-closing metathesis requires high dilution to avoid dimerization and as such it also needs long reaction times, a problematic issue when considering industrially application.…”

Section: Metathesismentioning

confidence: 99%

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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“…One of the known techniques that allow to increase the efficiency of metathesis catalysts is their portionwise or continuous slow addition to the reaction mixture. [36] In the next experiment (carried out according to the same Procedure "A," T = 50°C, p = 20 bar), catalyst Ru1 was added in four portions. First, 910 mL of EO together with 13 ppm of catalyst was placed in the reactor.…”

Section: Ethenolysis Of Technical Ethyl Oleatementioning

confidence: 99%

Non‐Glovebox Ethenolysis of Ethyl Oleate and FAME at Larger Scale Utilizing a Cyclic (Alkyl)(Amino)Carbene Ruthenium Catalyst

Kajetanowicz

Chwalba²,

Gawin³

et al. 2019

Euro J Lipid Sci & Tech

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A ruthenium metathesis catalyst Ru1 bearing a cyclic (alkyl)(amino)carbene (CAAC) ligand is used in the ethenolysis reaction of biosourced 90% pure undistilled ethyl oleate or technical fatty acid methyl esters mixture with grade 3 ethylene, to yield 1-decene and valuable terminal unsaturated 9-decenoic acid ester. Under optimized conditions (25 ppm of catalyst Ru1, 20 bar, 50°C, 2 h, use of metal scavenger/quenching agent, SnatchCat), the title reaction proceeds with high productivity (up to 70% conversion) and selectivity, and is tested in scale up to 1 L, with the exclusion of a glovebox or Schlenk techniques usage, and the ethenolysis products are isolated by fractional distillation. In addition, a large-scale synthesis of Ru1 is presented. Practical Applications: Decreasing availability of fossil organic feedstock and current policies of the European Union drives scientists to look for alternative sustainable sources of fine chemicals. In this context, olefin metathesis based ethenolysis of transesterified seed oils studied herein shows a significant potential as a sustainable way to obtain valuable products, such as 1-decene and valuable terminal unsaturated 9-decenoic acid ester. Unlike other published studies on ethenolysis, in the present work, the focus is on optimizing this reaction under industrially practical conditions, thus utilizing an air-stable catalyst, technical grade oleic substrates, grade 3 ethylene, and excluding the use of a glovebox or Schlenk techniques.

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

Cited by 31 publications

References 79 publications

Olefin Metathesis in Continuous Flow Reactor Employing Polar Ruthenium Catalyst and Soluble Metal Scavenger for Instant Purification of Products of Pharmaceutical Interest

Olefin Metathesis in Continuous Flow Reactor Employing Polar Ruthenium Catalyst and Soluble Metal Scavenger for Instant Purification of Products of Pharmaceutical Interest

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

Non‐Glovebox Ethenolysis of Ethyl Oleate and FAME at Larger Scale Utilizing a Cyclic (Alkyl)(Amino)Carbene Ruthenium Catalyst

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