Novel Intramolecular Rearrangement of Tertiary Propargylamine<i>N</i>-Oxides

Szabó, Anna; Hermecz, István

doi:10.1021/jo0104779

Cited by 16 publications

(16 citation statements)

References 26 publications

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“…[8] Thus, the scope of this rearrangement can be extended to N-oxides I where R 1 and R 2 form a morpholine, piperidine or pyrrolidine ring (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…[8] Excess of a nucleophilic base forces both rearrangements back drastically and brings about other reactions (Entry 5) not discussed here. Among others, product 6 was identified by GC-MS.…”

Section: Effect Of Basesmentioning

confidence: 98%

“…In response to base (triethylamine) addition, the amount of the acrylamide increased (Scheme 2). The base is thought to abstract a proton from the oxaziridine intermediate [8] (Scheme 1). These results led us to ascribe the acrylamide 3 and secondary amine 4 to the Meisenheimer route (B) for all three N-oxides 1aϪc.…”

Section: Kinetics Studiesmentioning

confidence: 99%

“…[7] We recently described a novel rearrangement of pargylin N-oxide (I: R 1 ϭ Bn; R 2 ϭ Me) in protic medium, leading to a new enamino aldehyde with the appearance of the secondary amine and a new acrylamide-type product in the reaction mixture. [8] We suggested possible mechanisms for these transformations: the enamino aldehyde major product is formed by an ionic mechanism through an isoxazoliniumtype intermediate state (route A), while the acrylamide byproduct results from the Meisenheimer rearrangement We have now extended these transformations to cyclic propargylamine N-oxides where R 1 and R 2 form a 5-or 6-membered ring, i.e. morpholine, piperidine, and pyrrolidine derivatives 1a, 1b, and 1c.…”

Section: Introductionmentioning

confidence: 99%

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Solvent‐Dependent Competitive Rearrangements of Cyclic Tertiary Propargylamine N‐Oxides

et al. 2004

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In protic media, cyclic propargylamine N‐oxides 1 undergo solvent‐dependent competitive rearrangements leading to enamino aldehydes 5, acrylamides 3, and secondary amines 4. The ratios of the products are evaluated and the possible mechanism of the competing reactions is interpreted by reaction kinetics studies and ab initio calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…[8] Thus, the scope of this rearrangement can be extended to N-oxides I where R 1 and R 2 form a morpholine, piperidine or pyrrolidine ring (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Section: Effect Of Basesmentioning

confidence: 98%

Section: Kinetics Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solvent‐Dependent Competitive Rearrangements of Cyclic Tertiary Propargylamine N‐Oxides

et al. 2004

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“…A general, effective, and simple synthesis of β-aminoenals was detailed based on the nucleophilic addition of secondary amines to 1,2,3-triazine ( 1 ) that complements the existing methods based on the condensation with malondialdehyde or its equivalents (1,1,3,3-tetramethoxypropane), 18 hydroamination of propargylic aldehyde, 19 or dehydrogenative amination of acrolein. 20 It is likely this general electrophilic character of 1,2,3-triazine and its ability to serve as a convenient equivalent of 2 may be extended to other classes of nucleophiles and such studies are in progress.…”

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confidence: 99%

Direct Synthesis of β-Aminoenals through Reaction of 1,2,3-Triazine with Secondary Amines

et al. 2017

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Simple and direct nucleophilic addition of secondary amines, including imidazole, to 1,2,3-triazine under mild reaction conditions (THF, 25–65 °C, 12–48 h), requiring no additives, cleanly provides β-aminoenals 4 in good yields (21 examples, 31–79%). The reaction proceeds by amine nucleophilic addition to C4 of the 1,2,3-triazine, in situ loss of N2, and subsequent imine hydrolysis to provide 4.

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Silver‐Catalyzed Transformation of Propargylic Amine N‐Oxides to Enones and Acyloxy Ketones via Isoxazolinium Intermediates

Cui¹,

Kung²,

Ko³

et al. 2014

Adv Synth Catal

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A novel silver-catalyzed transformation of propargylic amine N-oxides with switchable product profiles has been developed. A diversity of enones with excellent E/Z ratios (up to > 20:1) were obtained when the reactions were conducted in aprotic solvents. In contrast, 3-chlorobenzoxymethyl ketones and a-(3-chloro)-benzoxy enones were obtained by using protic solvents. Mechanistic studies suggested that in situ generated isoxazolinium ions are the key intermediates involved in these novel silver-catalyzed reaction pathways. Applications on the chemoselective modification of cysteine-containing peptides in aqueous medium have also been achieved. COMMUNICATIONS Jian-Fang Cui et al. Scheme 2. A proposed reaction mechanism.

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Novel Intramolecular Rearrangement of Tertiary PropargylamineN-Oxides

Cited by 16 publications

References 26 publications

Solvent‐Dependent Competitive Rearrangements of Cyclic Tertiary Propargylamine N‐Oxides

Solvent‐Dependent Competitive Rearrangements of Cyclic Tertiary Propargylamine N‐Oxides

Direct Synthesis of β-Aminoenals through Reaction of 1,2,3-Triazine with Secondary Amines

Silver‐Catalyzed Transformation of Propargylic Amine N‐Oxides to Enones and Acyloxy Ketones via Isoxazolinium Intermediates

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