Synthesis of 4-amino-5-allenylisoxazoles <i>via</i> gold(<scp>i</scp>)-catalysed propargyl aza-Claisen rearrangement

Tsuda, Masato; Morita, Taiki; Fukuhara, Shintaro; Nakamura, Hiroyuki

doi:10.1039/d0ob02544e

Cited by 11 publications

(1 citation statement)

References 46 publications

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“…4 In recent years, several methodologies for synthesizing allenes have been developed using transition metal catalyst like palladium, 5 copper, 6 and gold. 7 In the case of gold, the transformations generally involve isomerization of propargyl acetate derivatives, rearrangement of propargyl derivatives, and S N 2 reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I)

Rosales-Amezcua,

Ballinas-Indili,

López-Reyes

et al. 2024

J. Org. Chem.

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We have developed a straightforward and rapid methodology for the synthesis of tetrasubstituted allenes bearing carboxylic acids in the 1,3-position through the gold(I)-catalyzed nucleophilic addition of bis(trimethylsilyl)ketene acetals to ynones. The reaction was evaluated with several substrates, and 21 allenes were obtained in moderate to good yields. Using DFT calculations, we studied the mechanism of the reaction, which suggested a nucleophilic 1,4-addition pathway. The potential of allenes to act as a source of highly functionalized lactones was also explored.

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Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I)

Rosales-Amezcua,

Ballinas-Indili,

López-Reyes

et al. 2024

J. Org. Chem.

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Methylene Insertion into Nitrogen‐Heteroatom Single Bonds of 1,2‐Azoles via a Zinc Carbenoid: An Alternative Tool for Skeletal Editing

Tsuda,

Morita,

Morita

et al. 2023

Advanced Science

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The nitrogen‐heteroatom single bonds of 1,2‐azoles and isoxazolines underwent methylene insertion in the presence of CH2I2 (6 equiv.) and diethylzinc (3 equiv.) to produce a wide variety of the ring‐expanded six‐membered heterocycles. Density functional theory calculations suggest that the methylene insertion proceeds via cleavage of nitrogen‐heteroatom single bonds followed by ring closure.

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Gold‐Catalyzed Arylative Cope Rearrangement

Paroi,

Pegu,

Mane

et al. 2024

Angewandte Chemie

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Cope rearrangements have garnered significant attention owing to their ability to undergo structural reorganization in stereoselective manner. While substantial advances have been achieved over decades, these rearrangements remained applicable exclusively to parent 1,5‐hexadienes. Herein, we disclose the gold‐catalyzed arylative Cope rearrangement of 1,6‐heptadienes via a cyclization‐induced [3,3]‐rearrangement employing ligand‐enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross‐over experiment, HRMS analysis, 31P NMR and DFT studies have been performed to underpin the mechanism.

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Synthesis of 4-amino-5-allenylisoxazoles via gold(i)-catalysed propargyl aza-Claisen rearrangement

Abstract: Propargyl aza-Claisen rearrangement of 4-propargylaminoisoxazoles 1 proceeded in the presence of cationic gold(i) catalysts to give 4-amino-5-allenylisoxazoles 2 in good to high yields.

Cited by 11 publications

References 46 publications

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I)

Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I)

Methylene Insertion into Nitrogen‐Heteroatom Single Bonds of 1,2‐Azoles via a Zinc Carbenoid: An Alternative Tool for Skeletal Editing

Gold‐Catalyzed Arylative Cope Rearrangement

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