A Palladium‐Catalyzed Carbonylative–Deacetylative Sequence to 1,3‐Keto Amides

Nielsen, Dennis U.; Korsager, Signe; Lindhardt, Anders T.; Skrydstrup, Troels

doi:10.1002/adsc.201400545

Cited by 23 publications

(14 citation statements)

References 48 publications

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“…To this date, many CO‐surrogates have been explored for the application in “CO‐free” carbonylation . These suppliers include metal carbonyls such as [Mo(CO) 6 ],– [Cr(CO) 6 ], [W(CO) 5 ],– [Fe(CO) 5 ], acid chlorides (COgen, pivaloyl chloride), silacarboxylic acid, formates, formamides, formaldehyde, chloroform and oxalyl chloride . Generally, all these CO substitutes have been successfully applied in carbonylation reactions generating CO gas in situ or ex situ by using a two chamber reaction system .…”

Section: Methodsmentioning

confidence: 99%

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

et al. 2016

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A new protocol for the generation of carbon monoxide by the dehydration of glyoxylic acid has been developed. Glyoxylic acid was applied as an environmentally friendly and cheap substitute for toxic and gaseous CO in the palladium-catalyzed carbonylation reactions providing industrially interesting products in good to excellent yields.Carbon monoxide as an important chemical substance has found an application in many organic reactions. Especially, the transition-metal-catalyzed transformations [1] represent an elegant method for the efficient instalment of a carbonyl group into organic molecules providing various carboxylic acid derivatives, ketones and aldehydes, which are of relevant interest in the pharmaceutical and agrochemical industry. [2] However, the high toxicity of CO gas and the associated need for special handling considerably disadvantages the use of carbonylation strategies in laboratory and industrial environment. Such safety considerations has resulted in an increased demand for the development of new and laboratory-safer sources of CO. [3] To this date, many CO-surrogates have been explored for the application in "CO-free" carbonylation. [4][5][6][7][8][9][10][11][12] These suppliers include metal carbonyls such as [Mo(CO) 6 ], [4a-c] [Cr(CO) 6 ], [4d] [W(CO) 5 ], [4d-f] [Fe(CO) 5 ], [4g, h] acid chlorides [5] (COgen,[5a, b] pivaloyl chloride [5a] ), silacarboxylic acid, [6] formates, [7] formamides, [8] formaldehyde, [9] chloroform [10] and oxalyl chloride. [11] Generally, all these CO substitutes have been successfully applied in carbonylation reactions generating CO gas in situ or ex situ by using a two chamber reaction system. [5, 11] In terms of reaction efficiency and the avoidance of waste generation, a procedure for Heck, Songashira and radical carbonylation deserves a special attention. In method described by Ryu et al., [12] the carbon monoxide was generated ex situ by the Morgan reaction (dehydration of common and cheap formic acid with sulfuric acid). Recently, we have reported a reaction system for carbonylation of aryl halides using CO generated ex situ by Zn-mediated reduction of oxalyl chloride. [11c] A substoichiometric amount of CO-surrogate was sufficient for effective Pd-catalyzed carbonylative cou-plings. In our continuing effort to develop new carbonylation processes, [4g, h, 11c] we herein report a novel protocol for generation of CO gas and its direct application in palladium-catalyzed carbonylations. Two moles of carbon monoxide are generated in an efficient manner by dehydration of glyoxylic acid monohydrate using sulfuric acid.In 1907 H. D. Dakin [13] published a study describing the act of formaldehyde, glyoxylic acid and oxidizing substances on tryptophan and skatol (Hopkin-Cole test). He proposed a formation of glyoxylic acid by the oxidation of intermediary formed glycolaldehyde (Scheme 1, eq. 1). Despite the fact, that the formation of glyoxylic acid has not been satisfactory demonstrated, author suggested its theoretical decomposition to CO 2 , ...

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Section: Methodsmentioning

confidence: 99%

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

et al. 2016

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“…In recent years, transition‐metal‐catalyzed carbonylation reactions entailed the efficient and versatile synthesis of β ‐keto amides and esters. In 2014, the Skrydstrup group [91] used COgen as the CO source for Pd‐catalyzed carbonylative cross‐coupling between aryl/benzyl bromides and β ‐keto amides 152 in a two‐chamber reactor. After acidic work‐up, the carbonylation products 153 were deacetylated to β ‐keto amides 154 (Scheme 27).…”

Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

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“…This could be formed with two 13 C‐labeled carbonyls and be further cyclized in the presence of hydrazine to the double 13 C‐labeled pyrazole 83 . The deacetylation strategy has furthermore been used to access 1,3‐ketoamides as depicted in Scheme 20B . The [M+3]‐labeled dyclonine ( 85 ) could be synthesized by using 13 CO and LiAlD 4 as the isotope labeling sources and proceeding through the intermediate 1,3‐ketoamide 84 .…”

Section: C‐carbonylation Using [13c]comentioning

confidence: 99%

“…in Scheme 20B. 68 The [M+3]-labeled dyclonine (85) could be synthesized by using 13 CO and LiAlD 4 as the isotope labeling sources and proceeding through the intermediate 1,3-ketoamide 84.…”

Section: Carbonylative α-Arylations (C-c Bond Formation)mentioning

confidence: 99%

“…Positron emission tomography (PET) is a noninvasive molecular imaging technique, which is currently under rapid development. 100 Various positron-emitting isotopes are available, including 18 F, 15 O, 13 N, 11 C, 64 Cu, 89 Zr, and 68 Ga to mention some. 101,102 The given radioisotope is typically selected on the basis of half-life, synthetic strategy, and biochemical compatibility.…”

Section: Introductionmentioning

confidence: 99%

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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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A Palladium‐Catalyzed Carbonylative–Deacetylative Sequence to 1,3‐Keto Amides

Cited by 23 publications

References 48 publications

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

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

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A Palladium‐Catalyzed Carbonylative–Deacetylative Sequence to 1,3‐Keto Amides

Cited by 23 publications

References 48 publications

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

Glyoxylic Acid as a Carbon Monoxide Source for Carbonylation Reactions

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

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

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