Palladium-Catalyzed Insertion of CO<sub>2</sub> into Vinylaziridines: New Route to 5-Vinyloxazolidinones

Fontana, Francesco; Chen, Chia Chun; Aggarwal, Varinder K.

doi:10.1021/ol201193d

Cited by 99 publications

(47 citation statements)

References 45 publications

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“…Synthetic routes to oxazolidinone derivatives Several routes have been developedt os ynthesise oxazolidinone-based molecules, as shown in Scheme 5. [52] Propargylic starting materials in 1,2-dichloroethane (DCE) are efficiently converted into the corresponding oxazolidinones, oxazolidinthiones, imidazolidinthiones, and imidazolidinones using Pd(OAc) 2 and nBu 4 NOAc as catalysts, at room temperature (Scheme5d). [50] Iridium-complex-based amide activation in the presenceo fa weak phosphate base has been used to furnish ar eactive amidyl radical that readily adds to pendant alkenes to yield oxazolidinone derivatives (Scheme 5b).…”

Section: Oxazolidinonementioning

confidence: 99%

“…Intramolecular cyclisation of amino alcohol carbamates achieved by coppercatalysed cross-coupling with aryl iodides under mild conditions afforded N-aryl oxazolidinone derivatives( Scheme5a). [52] Oxazolidin-2-ones can be synthesised from phenyli socyanate and propargylic alcohols containingi nternala lkynes using ac ombination of silver acetate and N,N-dimethylaminopyridine(Scheme 5e). [51] AP d-catalysedr ingopeningcyclisation reaction of 2-vinylaziridines in the presence of carbon dioxide gives 5-vinyloxazolidinones (Scheme 5c).…”

Section: Oxazolidinonementioning

confidence: 99%

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The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Singh

Silakari

2018

ChemMedChem

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O-Heterocycles have been explored in the field of medicinal chemistry for a long time, but their significance has not been duly recognised and they are often shunned in favour of N-heterocycles. The design of bioactive molecules for nearly every pathophysiological condition is primarily focused on novel N-heterocycles. The main reasons for such bias include the ease of synthesis and possible mimicking of physiological molecules by N-heterocycles. But considering only this criterion rarely provides breakthrough molecules for a given disease condition, and instead the risks of toxicity or side effects are increased with such molecules. On the other hand, owing to improved synthetic feasibility, O-heterocycles have established themselves as equally potent lead molecules for a wide range of pathophysiological conditions. In the last decade there have been hundreds of reports validating the fact that equally potent molecules can be designed and developed by using O-heterocycles, and these are also expected to have comparably low toxicity. Even so, researchers tend to remain biased toward the use of N-heterocycles over O-heterocycles. Thus, this review provides a critical analysis of the synthesis and medicinal attributes of O-heterocycles, such as pyrones, oxazolones, furanones, oxetanes, oxazolidinones, and dioxolonones, and others, reported in the last five years, underlining the need for and the advantages guiding researchers toward them.

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Section: Oxazolidinonementioning

confidence: 99%

Section: Oxazolidinonementioning

confidence: 99%

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Singh

Silakari

2018

ChemMedChem

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“…. 114 Tetrabutylammonium difluorotriphenylsilicate adduct (TBAT) was required to hinder ion-pairing between the amide ion and the cationic Pd, thus increasing the yields of the products 203 and 204. The process is both regio-and stereoselective.…”

Section: Scheme 59mentioning

confidence: 99%

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Singh¹,

Sudheesh²,

Keroletswe³

2017

Arkivoc

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The inherent reactivity of the aziridine ring due to ring-strain makes it valuable building blocks for the synthesis of other heterocyclic motifs of biological relevance. Of particular significance is the generation of azomethine ylides from them and cycloaddition of ylides with alkenes, alkynes, and heterocumulenes. The ring undergoes opening followed by cyclization with a variety of reagents either in the presence of a catalyst or without any catalyst. This review article discusses the recent applications of aziridines in syntheses of four-to seven-membered heterocycles of biological relevance such as azetidines, 2

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“…Using LiI as catalyst, high yields (85-90%) were obtained for dialkyl-substituted aziridines with retention of the starting cis/trans stereochemistry. At a later stage, a binary catalytic system composed of palladium-dibenzylideneacetone [Pd 2 (dba) 3 ] and tetrabutylammonium difluorotriphenylsilicate (TBAT) was reported by Aggarwal and coworkers [108] to effectively convert 2-allyl-3-substituted aziridines to the corresponding oxazolidinones in mild conditions (0 C and 1 bar of CO 2 ); see Scheme 15. This Pd-mediated reaction proceeds with overall retention of configuration although the palladium intermediate can possibly isomerize to yield the product with opposite configuration.…”

Section: Insertion Of Co 2 Into An Aziridine Moietymentioning

confidence: 99%

Metal Complexes Catalyzed Cyclization with CO2

Rintjema

Carrodeguas

Laserna

et al. 2015

Topics in Organometallic Chemistry

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This chapter describes in general terms the catalytic methodology that has been made available for the use of carbon dioxide (CO 2 ) in cyclization reactions that incorporate an intact CO 2 fragment without changing the formal oxidation state of the carbon center. The major focus of this chapter will be on the most successful organometallic/inorganic complexes that have been used as catalyst systems throughout the last decade and the preferred ligand frameworks leading to elevated reactivity and/or selectivity behavior in CO 2 coupling reactions. Attention will be especially given to homogeneous catalyst systems as they have proven to be more versatile in CO 2 conversion catalysis and often have modular characteristics that allow for optimization of structure-activity relationships. The most important reactions that have been studied in the current context are designated CO 2 "addition" reactions to small molecule heterocycles such as epoxides and aziridines, though more recently other coupling partners such as diamines, dialcohols, and amino nitriles have further advanced the use of CO 2 in organic synthesis providing access to a wider range of structures. This chapter will serve to demonstrate the utility of CO 2 as a carbon reagent in the catalytic formation of the most prominent organic structures using cyclization strategies specifically.

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Palladium-Catalyzed Insertion of CO₂ into Vinylaziridines: New Route to 5-Vinyloxazolidinones

Abstract: 2-Vinylaziridines undergo a mild Pd-catalyzed ring-opening cyclization reaction with an ambient atmosphere of carbon dioxide to give 5-vinyloxazolidinones. The process is high yielding as well as regio- and stereoselective.

Cited by 99 publications

References 45 publications

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Metal Complexes Catalyzed Cyclization with CO2

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Palladium-Catalyzed Insertion of CO2 into Vinylaziridines: New Route to 5-Vinyloxazolidinones

Abstract: 2-Vinylaziridines undergo a mild Pd-catalyzed ring-opening cyclization reaction with an ambient atmosphere of carbon dioxide to give 5-vinyloxazolidinones. The process is high yielding as well as regio- and stereoselective.

Cited by 99 publications

References 45 publications

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Metal Complexes Catalyzed Cyclization with CO2

Contact Info

Product

Resources

About

Palladium-Catalyzed Insertion of CO₂ into Vinylaziridines: New Route to 5-Vinyloxazolidinones