Controlled generation and use of CO in flow

Hansen, Steffen V. F.; Wilson, Zoe E.; Ulven, Trond; Ley, Steven V.

doi:10.1039/c6re00020g

Cited by 27 publications

(20 citation statements)

References 24 publications

(29 reference statements)

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“…More recently,L ey and co-workers reporteda na lternative reactions ystem for generating CO within the tube-in-tube reactor (Scheme1b). [25] Oxalyl chloride (COCl) 2 (4)w as hydrolyzed by sodium hydroxide (NaOH)w ithin the outer channel of the tube-in-tube reactor.T he use of an Omnifitc olumn (0.68 mL) with two magnetic stirrer bars prior to the tube-intube reactorw as necessary to adequately mix the toluene phase containing COCl 2 and the aqueous NaOH phase. CO then passed through the membrane into the inner tube for the main organic transformation which was flowing counterflow to the CO generating stream.…”

Section: Carbonmonoxide (Co)mentioning

confidence: 99%

Membrane Microreactors for the On‐Demand Generation, Separation, and Reaction of Gases

Hone

Kappe

2020

Chemistry A European J

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The use of gases as reagents in organic synthesis can be very challenging, particularly at al aboratory scale. This Concept takes into account recent studies to make the case that gases can indeed be efficiently and safely formed from relativelyi nexpensive commercially available reagents for use in aw ide range of organic transformations. In particular,w ea rgue that the exploitation of continuous flow membrane reactorse nables the effective separation of the chemistry necessary for gas formation from the chemistry for gas consumption, with these two stages often containing incompatible chemistry. The approach outlined eliminates the need to store and transport excessive amountso fp otentially toxic, reactive or explosive gases.T he on-demand generation, separation and reaction of an umber of gases, including carbon monoxide, diazomethane, trifluoromethyl diazomethane, hydrogen cyanide, ammonia and formaldehyde, is discussed. Gas-Liquid Membrane Microreactors Over recent years, microreactors and continuous flow technologies have emergeda sa ne nabling tool for the safe handling of hazardousc hemistry. [8, 9] In particular, for accessing "forgotten" and "forbidden" chemistry which cannotb ea ccessed under conventional batch conditions.

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Section: Carbonmonoxide (Co)mentioning

confidence: 99%

Membrane Microreactors for the On‐Demand Generation, Separation, and Reaction of Gases

Hone

Kappe

2020

Chemistry A European J

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“…A 'tube-in-tube' reactor was also utilised in the controlled generation and use of carbon monoxide in Pd-catalysed carbonylation reactions by Ley et al 40 The generation of CO was achieved by safe hydrolysis of oxalyl chloride using an aqueous NaOH solution in the first part of the flow reactor setup. The 'tube-in-tube' reactor was used to enrich a reaction stream with CO in the second part of the flow platform.…”

Section: Scheme 25 Flow Carbonylation Of Sterically Hindered Ortho-sumentioning

confidence: 99%

Recent Applications of Continuous Flow in Homogeneous Palladium Catalysis

Markovič¹,

Lopatka²,

Gracza³

et al. 2020

Synthesis

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Considerable advances have been made using continuous flow chemistry as an enabling tool in organic synthesis. Consequently, the number of articles reporting continuous flow methods has increased significantly in recent years. This review covers the progress achieved in homogeneous palladium catalysis using continuous flow conditions over the last five years, including C–C/C–N cross-coupling reactions, carbonylations and reductive/oxidative transformations.1 Introduction2 C–C Cross-Coupling Reactions3 C–N Coupling Reactions4 Carbonylation Reactions5 Miscellaneous Reactions6 Key to Schematic Symbols7 Conclusion

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“…The tube‐in‐tube flow reactor was successfully applied for hydroformylation and some carbonylation reactions but not specifically for reductive carbonylation reactions . Furthermore, Ley and co‐workers recently showed that oxalyl chloride can be hydrolyzed by using NaOH to form CO in situ in flow and subsequently used the generated CO in carbonylation reactions . The aforementioned strategies are good options for research‐scale experimentation; however, both approaches suffer from limited scalability in terms of atom inefficiency, poorer performance at scale‐up, or are simply too expensive …”

Section: Introductionmentioning

confidence: 99%

“…[14] Furthermore, Ley and co-workersr ecently showed that oxalyl chloridec an be hydrolyzed by using NaOH to form CO in situ in flow and subsequently used the generatedC Oi nc arbonylation reactions. [15] The aforementioned strategies are good options for research-scale experimentation; however, both approaches suffer from limited scalability in terms of atom inefficiency,p oorer performance at scale-up, or are simply too expensive. [16,17] Tubular plug flow reactors have emerged as ap latform for the safe, efficient, and scalable utilization of gases direct from gas cylinders by using mass-flow controllers.…”

Section: Introductionmentioning

confidence: 99%

Continuous‐flow Synthesis of Aryl Aldehydes by Pd‐catalyzed Formylation of Aryl Bromides Using Carbon Monoxide and Hydrogen

et al. 2018

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A continuous‐flow protocol utilizing syngas (CO and H 2 ) was developed for the palladium‐catalyzed reductive carbonylation of (hetero)aryl bromides to their corresponding (hetero)aryl aldehydes. The optimization of temperature, pressure, catalyst and ligand loading, and residence time resulted in process‐intensified flow conditions for the transformation. In addition, a key benefit of investigating the reaction in flow is the ability to precisely control the CO‐to‐H 2 stoichiometric ratio, which was identified as having a critical influence on yield. The protocol proceeds with low catalyst and ligand loadings: palladium acetate (1 mol % or below) and cata CX ium A (3 mol % or below). A variety of (hetero)aryl bromides at a 3 mmol scale were converted to their corresponding (hetero)aryl aldehydes at 12 bar pressure (CO/H 2 =1:3) and 120 °C reaction temperature within 45 min residence time to afford products mostly in good‐to‐excellent yields (17 examples). In particular, a successful scale‐up was achieved over 415 min operation time for the reductive carbonylation of 2‐bromo‐6‐methoxynaphthalene to synthesize 3.8 g of 6‐methoxy‐2‐naphthaldehyde in 85 % isolated yield. Studies were conducted to understand catalyst decomposition within the reactor by using inductively coupled plasma–mass spectrometry (ICP–MS) analysis. The palladium could easily be recovered using an aqueous nitric acid wash post reaction. Mechanistic aspects and the scope of the transformation are discussed.

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Controlled generation and use of CO in flow

Abstract: A tube-in-tube flow reactor allows the generation and immediate use of CO, without the need for CO cylinders.

Cited by 27 publications

References 24 publications

Membrane Microreactors for the On‐Demand Generation, Separation, and Reaction of Gases

Membrane Microreactors for the On‐Demand Generation, Separation, and Reaction of Gases

Recent Applications of Continuous Flow in Homogeneous Palladium Catalysis

Continuous‐flow Synthesis of Aryl Aldehydes by Pd‐catalyzed Formylation of Aryl Bromides Using Carbon Monoxide and Hydrogen

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