Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

Natte, Kishore; Dumrath, Andreas; Neumann, Helfried; Beller, Matthias

doi:10.1002/ange.201404833

Cited by 50 publications

(11 citation statements)

References 53 publications

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“…[9][10][11][12][13][14] For example, Manabe and co-workers [15] adopted Nformylsaccharin as ah ighly reactive CO surrogate and silane as ah ydrogen donor,a nd therebyr ealized reductivec arbonylation of aryl bromides to aryl aldehydes catalyzed by palladium acetate with the aid of al igand and ab ase (Scheme 1a). Subsequently,o ther CO surrogates, including isocyanide [16] and paraformaldehyde, [17] were successfully appliedi nt he carbonylation of aryl/hetaryl iodidesa nd bromides in the presence of different silanes, providing access to aw ide range of aryl/hetaryl aldehydes under relatively mild conditions (Scheme 1b, c). Although great progress has been made in the use of Pdcatalyzed CO-free carbonylation of aromatic halidest os ynthe-size aryl(hetaryl)a ldehydes, there are still inherentd rawbacks, such as the need for expensive CO surrogates and ligands, and inevitable by-product formation.…”

Section: Introductionmentioning

confidence: 99%

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Yang

Zhao

et al. 2015

Chemistry A European J

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The formylation of aryl halides with CO2 to generate aryl aldehydes is challenging. Herein, we report a novel synthesis of aryl aldehydes by formylation of aryl bromides with CO2 and a waste silane, poly(methylhydrosiloxane) (PMHS). It has been discovered that a simple combination of 1,3-bis(diphenyphosphino)propane (DPPP)-chelated Pd catalyst, Pd(DPPP)Cl2 , with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is able to effectively catalyze the reaction, leading to aryl aldehydes in moderate to excellent yields, and without any by-products in most cases. Moreover, this route could be extended to the formylation of aryl iodides with high efficiency. This approach is simple, less costly, and environmentally friendly, and also widens the applications of CO2 to form value-added chemicals by the construction of new C-C bonds.

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Section: Introductionmentioning

confidence: 99%

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Yang

Zhao

et al. 2015

Chemistry A European J

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“…Thus, the use of convenient reagents for selective methylation of life science molecules continues to be an important goal. In this regard, paraformaldehyde 40 – 42 , which is stable and easy to handle, can be a suitable methylation reagent.…”

Section: Introductionmentioning

confidence: 99%

Convenient iron-catalyzed reductive aminations without hydrogen for selective synthesis of N-methylamines

et al. 2017

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N-Methylated amines play an important role in regulating the biological and pharmaceuticalproperties of all kinds of life science molecules. In general, this class of compounds is synthesized via reductive amination reactions using high pressure of molecular hydrogen. Thus, on laboratory scale especially in drug discovery, activated (toxic) methyl compounds such as methyl iodide and dimethyl sulfate are still employed, which also generate significant amounts of waste. Therefore, the development of more convenient and operationally simple processes for the synthesis of advanced N-methylamines is highly desired. Herein, we report the synthesis of functionalized and structurally diverse N-methylamines directly from nitroarenes and paraformaldehyde, in which the latter acts as both methylation and reducing agent in the presence of reusable iron oxide catalyst. The general applicability of this protocol is demonstrated by the synthesis of >50 important N-methylamines including highly selective reductive N-methylations of life science molecules and actual drugs, namely hordenine, venlafaxine, imipramine and amitriptyline.

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“…The first example on using paraformaldehyde as a CORM for Pd‐catalyzed carbonylation chemistry was published by Beller and coworkers in 2014. In the presence of a large excess of [ 13 C ]paraformaldehyde, a 13 C‐labeled ester ( 102 ) and an aldehyde ( 103 ) could be synthesized by using either methanol or a silane, respectively, as the nucleophile in the presence of a similar Pd‐catalyst system (Scheme 26A).…”

Section: C‐carbonylation Using [13c]comentioning

confidence: 99%

Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO

Nielsen

Neumann

Lindhardt

et al. 2018

Labelled Comp Radiopharmac

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Carbon monoxide represents the most important C1-building block for the chemical industry, both for the production of bulk and fine chemicals, but also for synthetic fuels. Yet its toxicity and subsequently its cautious handling have limited its applications in medicinal chemistry research and in particular for the synthesis of pharmaceutically relevant molecules. Recent years have nevertheless witnessed a considerable headway on the development of carbon monoxide surrogates and reactor systems, which provide an ideal setting for performing carbonylation chemistry with stoichiometric and substoichiometric carbon monoxide. Such setups are particularly ideal for the introduction of isotope labels such as carbon-11, carbon-13, and carbon-14 into bioactive compounds. This review summarizes this growing field and examines the large number of carbonylation reactions that can be exploited for the introduction of a carbon isotope.

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Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

Cited by 50 publications

References 53 publications

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Convenient iron-catalyzed reductive aminations without hydrogen for selective synthesis of N-methylamines

Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO

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Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

Cited by 50 publications

References 53 publications

An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane)

Convenient iron-catalyzed reductive aminations without hydrogen for selective synthesis of N-methylamines

Recent developments in carbonylation chemistry using [13C]CO, [11C]CO, and [14C]CO

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About

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO