Catalytic Enantioselective Inverse Electron Demand Hetero‐Diels–Alder Reaction with Allylsilanes

Matsumura, Yuki; Suzuki, Takahiro; Sakakura, Akira; Ishihara, Kazuaki

doi:10.1002/ange.201402934

Cited by 12 publications

(2 citation statements)

References 56 publications

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“…[55] The Ishihara group hasd eveloped ac hiral copper catalyst to enable enantioselective hetero-iEDDAr eactions between keto esters and allylsilanes. [56] Feng et al have also developedacopper catalystb yu sing chiral N,N'-dioxide-metal complex 51 [57] to control the competing hetero-iEDDA reaction and the Diels-Alder reaction between cyclopentadiene (50)a nd a,b-unsaturated carbonyl compounds such as 49 ( Figure 13) with good control over selectivity.D iels-Alderp roduct 52 is favored at room temperature, whereas hetero-iEDDAp roduct 53 is favored at al ow temperature of approximately À20 8Cf or aw ide variety of substituents.…”

Section: Metal-catalyzed Iedda Reactionsmentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Png

Zeng

et al. 2017

Chemistry An Asian Journal

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Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas.

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Section: Metal-catalyzed Iedda Reactionsmentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Png

Zeng

et al. 2017

Chemistry An Asian Journal

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“…A broad substrate scope was carried out furnishing the product 1492 in up to 99% yield and 99% ee in a 92:8 cis / trans ratio. 539 It was also applied in the asymmetric Cu-catalyzed Diels–Alder reaction to great effect. 540 …”

Section: Tetradentate Bis(oxazoline) Ligandsmentioning

confidence: 99%

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

et al. 2021

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The chiral oxazoline motif is present in many ligands that have been extensively applied in a series of important metal-catalyzed enantioselective reactions. This Review aims to provide a comprehensive overview of the most significant applications of oxazoline-containing ligands reported in the literature starting from 2009 until the end of 2018. The ligands are classified not by the reaction to which their metal complexes have been applied but by the nature of the denticity, chirality, and donor atoms involved. As a result, the continued development of ligand architectural design from mono(oxazolines), to bis(oxazolines), to tris(oxazolines) and tetra(oxazolines) and variations thereof can be more easily monitored by the reader. In addition, the key transition states of selected asymmetric transformations will be given to illustrate the features that give rise to high levels of asymmetric induction. As a further aid to the reader, we summarize the majority of schemes with representative examples that highlight the variation in % yields and % ee s for carefully selected substrates. This Review should be of particular interest to the experts in the field but also serve as a useful starting point to new researchers in this area. It is hoped that this Review will stimulate both the development/design of new ligands and their applications in novel metal-catalyzed asymmetric transformations.

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Stereoselective Synthesis of Hydropyrano[3,2‐b]indoles via Organocatalytic Asymmetric Inverse‐Electron‐Demand Oxa‐Diels–Alder Reaction

Yang

Huang

et al. 2016

Adv Synth Catal

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Enantio‐ and diastereoselective inverse‐electron‐demand oxa‐Diels–Alder reactions are described between (Z)‐2‐ylideneoxindoles and aldehydes in the presence of a chiral secondary amine catalyst. The corresponding hydropyrano[3,2‐b]indoles are produced in up to 77% yield with up to 99% ee. Convenient synthetic transformations of the products readily lead to pharmacologically interesting scaffolds bearing multiple functional groups. This method may also provide an alternative approach for the asymmetric synthesis of 2‐spirocyclo‐3‐oxindoles.

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Catalytic Enantioselective Inverse Electron Demand Hetero‐Diels–Alder Reaction with Allylsilanes

Cited by 12 publications

References 56 publications

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

Stereoselective Synthesis of Hydropyrano[3,2‐b]indoles via Organocatalytic Asymmetric Inverse‐Electron‐Demand Oxa‐Diels–Alder Reaction

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