Modernized Low Pressure Carbonylation Methods in Batch and Flow Employing Common Acids as a CO Source

Brancour, Célia; Fukuyama, Takahide; Mukai, Yu; Skrydstrup, Troels; Ryu, Ilhyong

doi:10.1021/ol401092a

Cited by 153 publications

(84 citation statements)

References 53 publications

(16 reference statements)

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“…[6] Additionally, olefin carbonylation reactions in the presence of formic acid as a carbonyl source are also achieved through sequential dehydrogenation and reverse water gas shift processes at elevated temperature (> 150 8C). [7] Moreover, formates (F; R = alkyl, aryl) [8] and formamides (G) [9] have also been used for the carbonylation of olefins and aryl halides.…”

mentioning

confidence: 99%

Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

et al. 2015

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In recent years, considerable effort has focused on the development of novel carbonylative transformations using CO surrogates. Consequently, toxic CO gas can be replaced by more convenient inorganic or organic carbonyl compounds. Herein, the first regioselective methoxycarbonylation of alkenes with paraformaldehyde and methanol as CO substitutes is reported. This new procedure is applicable to a series of alkenes in the presence of a palladium catalyst under relatively mild conditions and is highly atom efficient.

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confidence: 99%

Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

et al. 2015

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“…In addition, since some CO surrogates developed in our laboratory are now commercially available at reasonable prices, 104) they have begun to be applied in the fields of medicinal chemistry, 105,106) total syntheses of natural bioactive compounds, 107,108) and flow chemistry. 109,110) For the development of truly useful reactions, the practical aspects of the organic reactions in question need to be considered during their development and application. The substitution of toxic gases for their surrogates in synthetic organic reactions is attractive; the resulting ready-to-use reactions may result in paradigm-shifting protocols for conducting reactions with toxic gases.…”

Section: Resultsmentioning

confidence: 99%

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

Konishi

2018

Chem. Pharm. Bull.

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The use of toxic gas surrogates in organic reactions instead of the gas itself contributes to enhancing the safety, practicality, and efficiency of the reactions involved. Our efforts toward the creation of toxic gas surrogates and the development of a series of catalytic reactions using these surrogates are described. Improvements in substrate scope during the hydroesterification of alkenes using formates facilitated by the Ru-imidazole catalyst system provided the opportunity to discover that phenyl formate is a useful carbon monoxide (CO) surrogate for the generation of CO and phenol under weakly basic conditions. This discovery triggered the development of highly reactive but stable CO surrogates and a variety of Pd-catalyzed carbonylative transformations. N-Formylsaccharin facilitated the use of additional nucleophiles in carbonylation reactions that provided access to a variety of carbonyl compounds. Detailed experimental and theoretical mechanistic studies into the generation of CO from phenyl formate suggest that CO generation proceeds via a concerted E2 α-elimination. Furthermore, a known surrogate of sulfur dioxide was applied for the first time to the selective syntheses of cyclic sulfonamides and sulfinamides, confirming that the surrogate operates as an "S O" source. Notably, the reactions described herein are scalable and can be performed without the use of external toxic gases and specialized reaction vessels; they are easy and simple to perform and demonstrate enormous potential for industrial application.

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“…[186] Ryu and co-workers described the generation and consumption of carbon monoxide in at ube-in-tube reactor. [187] Thei nner tube was made of gas-permeable Te flon AF2400, while the outer tube was made of stainless steel. Carbon monoxide was generated in the inner tube by dehydration of formic acid in sulfuric acid at elevated temperatures (Morgan reaction).…”

Section: Flow Chemistrymentioning

confidence: 99%

“…1mmol per day). [187] Scheme 51. Continuous-flow decarbonylation of aldehydes using N 2 as as tripping gas.…”

Section: Flow Chemistrymentioning

confidence: 99%

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Continuous‐Flow Technology—A Tool for the Safe Manufacturing of Active Pharmaceutical Ingredients

Gutmann¹,

Cantillo²,

Kappe³

2015

Angew Chem Int Ed

1,265

676

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In the past few years, continuous-flow reactors with channel dimensions in the micro- or millimeter region have found widespread application in organic synthesis. The characteristic properties of these reactors are their exceptionally fast heat and mass transfer. In microstructured devices of this type, virtually instantaneous mixing can be achieved for all but the fastest reactions. Similarly, the accumulation of heat, formation of hot spots, and dangers of thermal runaways can be prevented. As a result of the small reactor volumes, the overall safety of the process is significantly improved, even when harsh reaction conditions are used. Thus, microreactor technology offers a unique way to perform ultrafast, exothermic reactions, and allows the execution of reactions which proceed via highly unstable or even explosive intermediates. This Review discusses recent literature examples of continuous-flow organic synthesis where hazardous reactions or extreme process windows have been employed, with a focus on applications of relevance to the preparation of pharmaceuticals.

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Modernized Low Pressure Carbonylation Methods in Batch and Flow Employing Common Acids as a CO Source

Cited by 153 publications

References 53 publications

Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

Continuous‐Flow Technology—A Tool for the Safe Manufacturing of Active Pharmaceutical Ingredients

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