Multicomponent Catalytic Enantioselective Synthesis of Isoxazolidin‐5‐Ones

Annibaletto, Julien; Martzel, Thomas; Levacher, Vincent; Oudeyer, Sylvain; Brière, Jean‐François

doi:10.1002/adsc.202100719

“…The substance afforded through the Kinetic Monte Carlo (KMC) process by the enantioselective reaction of diisopropylhydroxyurea 58, Meldrum's acid 1, and aldehyde 13 involving cupreine organocatalyst (Scheme 29). [42] 3. Synthesis of six-membered heterocycles…”

Section: N-and O-heterocyclic Compoundsmentioning

confidence: 99%

The Molecular Diversity Scope of Meldrum's Acid in Multicomponent Reactions

Ziarani,

Ebrahimi,

Mohajer

et al. 2023

ChemistrySelect

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Multicomponent reactions (MCRs) have gained significant attention in the field of organic synthesis due to their ability to efficiently construct complex molecular structures in a single step. Among the reagents employed in MCRs, Meldrum's acid has emerged as a highly versatile and valuable starting material, offering a wide range of molecular diversity. This comprehensive review explores the molecular diversity scope of Meldrum's acid in various MCRs, focusing on its unique attributes and the greener aspects of its application. Meldrum's acid possesses several remarkable features that contribute to its suitability as a key component in MCRs. Its high acidity enables effective participation in a variety of chemical reactions, while its rigid structure provides stability and allows for precise control of the reaction pathways. Furthermore, the ability of Meldrum's acid to undergo both nucleophilic and electrophilic attacks makes it highly versatile in the construction of diverse molecular frameworks. Its low steric hindrance further enhances its reactivity, facilitating efficient bond formation. By surveying the literature from the last five years (2018–2022), we delve into the broad range of applications of Meldrum's acid in MCRs. The review encompasses the synthesis of various heterocyclic compounds, highlighting the significance of Meldrum's acid in achieving molecular diversity. Moreover, particular emphasis is placed on the greener aspects of utilizing Meldrum's acid, considering the growing demand for environmentally friendly synthetic approaches. This includes exploring greener solvents, milder reaction conditions, and reduced waste generation.

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Locking the Conformation of a Paddlewheel Rhodium Complex: Design, Synthesis, and Applications in Catalytic Nitrene Transfers

Tang,

Noda,

Shibasaki

2023

Angewandte Chemie

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The exponential proliferation of conformers makes it impossible to examine the entire population in most systems. Controlling conformational ensembles is thus pivotal in many areas of chemistry. Rh2(esp)2, a dicarboxylate‐derived paddlewheel rhodium complex, is one of the most effective catalysts for nitrene chemistry. Its enormous success has led to preparing many analogous complexes. However, there has been little consideration for the conformational dynamics of the parent catalyst. Herein, we report a new ligand modification principle that prevents conformer interconversion. The resulting complex comprises two isolable conformers, whose structures have been determined by X‐ray diffraction. Combined experimental and computational data has revealed similarities and dissimilarities between the conformationally confined and parent complexes. Three model cases have demonstrated the utility of conformational fixation in the development of stereoselective catalysts for nitrene transfer reactions. The design principle described in this study can be combined with other established modification strategies, serving as a springboard for further advancement of the chemistry of paddlewheel metal complexes.

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Locking the Conformation of a Paddlewheel Rhodium Complex: Design, Synthesis, and Applications in Catalytic Nitrene Transfers

Tang,

Noda,

Shibasaki

2023

Angew Chem Int Ed

2

0

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The exponential proliferation of conformers makes it impossible to examine the entire population in most systems. Controlling conformational ensembles is thus pivotal in many areas of chemistry. Rh2(esp)2, a dicarboxylate‐derived paddlewheel rhodium complex, is one of the most effective catalysts for nitrene chemistry. Its enormous success has led to preparing many analogous complexes. However, there has been little consideration for the conformational dynamics of the parent catalyst. Herein, we report a new ligand modification principle that prevents conformer interconversion. The resulting complex comprises two isolable conformers, whose structures have been determined by X‐ray diffraction. Combined experimental and computational data has revealed similarities and dissimilarities between the conformationally confined and parent complexes. Three model cases have demonstrated the utility of conformational fixation in the development of stereoselective catalysts for nitrene transfer reactions. The design principle described in this study can be combined with other established modification strategies, serving as a springboard for further advancement of the chemistry of paddlewheel metal complexes.

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Multicomponent Catalytic Enantioselective Synthesis of Isoxazolidin‐5‐Ones

Cited by 3 publications

References 68 publications

The Molecular Diversity Scope of Meldrum's Acid in Multicomponent Reactions

The Molecular Diversity Scope of Meldrum's Acid in Multicomponent Reactions

Locking the Conformation of a Paddlewheel Rhodium Complex: Design, Synthesis, and Applications in Catalytic Nitrene Transfers

Locking the Conformation of a Paddlewheel Rhodium Complex: Design, Synthesis, and Applications in Catalytic Nitrene Transfers

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