Reactivity of allenoates towards aziridines: synthesis of functionalized methylenepyrrolidines and pyrroles

Laia, Fernanda M. Ribeiro; Cardoso, António J. Marques; Beja, Α. Matos; Silva, Manuela Ramos; Melo, Teresa M. V. D. Pinho e

doi:10.1016/j.tet.2010.09.081

Cited by 22 publications

(11 citation statements)

References 22 publications

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“…58,59 The preference for cleavage depends on substitution pattern of aziridines, and solvent used. In a recent communication, Laia and Pinho e Melo have reported the thermal reactivity of an alkyne or allene-bearing aziridines, derived from salicylaldehyde.…”

Section: Scheme 24mentioning

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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Section: Scheme 24mentioning

confidence: 99%

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Singh¹,

Sudheesh²,

Keroletswe³

2017

Arkivoc

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Section: Introductionmentioning

confidence: 99%

“…The chemistry of allenes has been one of our research topics. − Particularly interesting was the study on the reactivity of allenoates toward aziridines in organic solvents, under microwave irradiation (MW) or conventional heating, and in supercritical carbon dioxide (scCO 2 ) . It was observed that aziridine-2-carboxylates react with allenoates to give 4-methylenepyrrolidines (e.g., 3 ) exclusively, via 1,3-dipolar cycloaddition of the in situ generated azomethine ylides . Interestingly, allenoates can also participate in [3 + 2] cycloaddition with 2-benzoylaziridines as the 2π component to afford 4-methylenepyrrolidines (e.g., 3 ), but they can also react through formal [3 + 2] cycloaddition via aziridine C–N bond cleavage leading to functionalized pyrroles (e.g., 5 ) (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

“…N -Cyclohexyl-2-benzoyl-3-phenylaziridines reacted with buta-2,3-dienoates to give pyrroles as the major or exclusive product. Bulkier N-substituents on the aziridine ring favor the formal [3 + 2] cycloadditions with allenoates leading to selective formation of pyrroles . In contrast, performing the same reactions under scCO 2 conditions affords pyrroles 5 as single products regardless of the aziridine N-substituent .…”

Section: Introductionmentioning

confidence: 99%

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(1H-Tetrazol-5-yl)-Allenes: Building Blocks for Tetrazolyl Heterocycles

et al. 2016

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(1H-Tetrazol-5-yl)-allenes have been prepared for the first time, and their reactivity toward aziridines explored. Reaction of a (1-benzyl-1H-tetrazol-5-yl)-phosphonium chloride and acyl chlorides in the presence of triethylamine afforded the target allenes via Wittig reaction of the in situ generated phosphorus ylide and ketenes. 1-(1-Benzyl-1H-tetrazol-5-yl)propa-1,2-diene and 3-methyl-, 3-ethyl- and 3-benzyl derivatives undergo microwave-induced formal [3 + 2] cycloaddition with cis-N-benzyl-2-benzoyl-3-phenylaziridine, through C-N bond cleavage, to give selectively tetrasubstituted pyrroles. In contrast, with (1H-tetrazol-5-yl)-allenes bearing bulkier substituents at C-3, such as i-propyl or a tert-butyl, 4-methylenepyrrolidines were obtained exclusively via [3 + 2] cycloaddition of the in situ generated azomethine ylide. The latter allenes also gave 4-methylenepyrrolidines on reacting with cis-2-benzoyl-N-cyclohexyl-3-phenylaziridine, whereas with the other allenes, pyrroles were obtained as major products together with the formation of 4-methylenepyrrolidines. All the studied (1H-tetrazol-5-yl)-allenes reacted with N-benzyl-cis-3-phenylaziridine-2-carboxylate to give the corresponding 4-methylenepyrrolidines exclusively.

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“…As nitrogen-based 1,3-dipoles, they play important roles in organic synthesis, particularly in cycloadditions [7,8,9,10]. Nitrogen ylides have been used to achieve (3 + 2) annulation [11,12,13,14,15] and (3 + 3) annulation [16,17], providing a direct route to various nitrogen-containing heterocycles, including pyrrolidine [18,19,20,21,22], piperidine [23,24], and piperazine [25]. This strategy has proven powerful for synthesizing natural products as well as other biologically interesting compounds [26,27,28,29].…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthesis of Fully Substituted Pyrrolidine-Fused 3-Spirooxindoles via 1,3-Dipolar Cycloaddition of Aziridine and 3-Ylideneoxindole

et al. 2016

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Drug-like spirocyclic scaffolds have been prepared by fusing fully functionalized pyrrolidine with oxindoles in an approach based on 1,3-dipolar cycloaddition. Reaction between aziridine and 3-ylideneoxindole generated diverse spirooxindole-pyrrolidines in good yield (up to 95%) with high diastereoselectivity (up to >20:1). The reaction also proceeded smoothly with several other synthetically useful activated trisubstituted olefins. The mild reaction conditions, short reaction times, and high tolerance for various substitutions make this approach attractive for constructing pharmacologically interesting spiro-architectures.

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Reactivity of allenoates towards aziridines: synthesis of functionalized methylenepyrrolidines and pyrroles

Cited by 22 publications

References 22 publications

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

(1H-Tetrazol-5-yl)-Allenes: Building Blocks for Tetrazolyl Heterocycles

Efficient Synthesis of Fully Substituted Pyrrolidine-Fused 3-Spirooxindoles via 1,3-Dipolar Cycloaddition of Aziridine and 3-Ylideneoxindole

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