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

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

doi:10.1002/anie.201402934

Cited by 61 publications

(30 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Evan and co‐workers have developed enantioselective, chiral oxazoline–copper(II) catalysts for hetero‐iEDDA reactions between acyl phosphonates and enol ethers and for the preparation of dihydropyrans . The Ishihara group has developed a chiral copper catalyst to enable enantioselective hetero‐iEDDA reactions between keto esters and allylsilanes . Feng et al.…”

Section: Mechanistic Studies Of the Iedda Reactionmentioning

confidence: 99%

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

Png

Zeng

et al. 2017

Chemistry An Asian Journal

View full text Add to dashboard Cite

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.

show abstract

Section: Mechanistic Studies Of the Iedda Reactionmentioning

confidence: 99%

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

Png

Zeng

et al. 2017

Chemistry An Asian Journal

View full text Add to dashboard Cite

show abstract

“…2a ) 13 . Later, Ishihara and co-workers disclosed that bis(oxazoline)/copper(II) species could promote the enantioselective hetero-Diels–Alder (HDA) reaction of β,γ-unsaturated ketoesters with allyl silanes 14 . In addition, Zhang and co-workers demonstrated that the same β,γ-unsaturated ketoester substrates could react with vinylindoles in the presence of an imidodiphosphoric acid to produce [4 + 2] cycloadducts 15 .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective access to tricyclic tetrahydropyran derivatives by a remote hydrogen bonding mediated intramolecular IEDHDA reaction

Jin

Tang

et al. 2021

Nat Commun

View full text Add to dashboard Cite

Inverse-electron-demand-hetero-Diels-Alder reactions of alkenes with α,β-unsaturated keto compounds allow rapid access to the tetrahydropyran ring found in numerous natural products and bioactive molecules. Despite its synthetic interest, catalytic asymmetric versions of this process remain underdeveloped, especially regarding the use of non-activated alkenes reacting with α,β-unsaturated ketone or aldehyde, for which no report can be found in the literature. Herein, we describe the catalytic inverse-electron-demand-hetero-Diels-Alder reactions between neutral alkenes and an α,β-unsaturated ketones or aldehydes to produce a variety of trans-fused [5,6,8] tricyclic structures containing a central, chiral tetrahydropyran ring. This complex transformation, which is achieved using a chiral phosphoric acid, allows for the formation of four stereogenic centers in a single step with high regio-, diastereo- and enantioselectivity (up to 99% ee). Such level of stereocontrol could be achieved by a key remote double hydrogen atom bonding interaction between the linear substrate and the catalyst.

show abstract

“…To the best of our knowledge, Snapper′s group first described a Cu(OTf) 2 /box catalyzed 1,4‐conjugate addition of allyltrimethylsilane to activated cyclic enones without control of the diastereoselectivity owing to keto‐enol tautomerism of products (Scheme 1.2 c) [7e] . Moreover, as less nucleophilic alkenes, allylsilanes have been employed in annulations [8] and hetero‐Diels–Alder (HDA) reactions [9] . In this regard, the group of Franz described the only example of asymmetric catalytic allylsilane carboannulation with alkylidene oxindoles by the use of the Sc III /indapybox complex as the catalyst (Scheme 1.2 b) [8b] .…”

Section: Introductionmentioning

confidence: 99%

“…In this regard, the group of Franz described the only example of asymmetric catalytic allylsilane carboannulation with alkylidene oxindoles by the use of the Sc III /indapybox complex as the catalyst (Scheme 1.2 b) [8b] . In 2014, Ishihara, Sakakura, and co‐workers established the unique catalytic enantioselective HDA reaction of allylsilanes to β,γ‐unsaturated α‐ketoesters (Scheme 1.2 d) [9] . Despite these advances, the development of new asymmetric reactions with allylsilanes is still highly desirable.…”

Section: Introductionmentioning

confidence: 99%

Allylsilane Reagent‐Controlled Divergent Asymmetric Catalytic Reactions of 2‐Naphthoquinone‐1‐methide

Lin

Liu

2020

Chemistry A European J

View full text Add to dashboard Cite

Herein, the first allylsilane reagent‐controlled divergent asymmetric Hosomi–Sakurai conjugate allylation and hetero‐Diels–Alder (HDA) with 2‐naphthoquinone‐1‐methide (2‐Nap‐Q‐1‐M) under the catalysis of ScIII/Feng ligand complex is reported. With these methods, a variety of uniquely substituted chiral allyl‐functionalized diaryl compounds and naphthopyran products were obtained in a straightforward and highly stereoselective (up to 96.5:3.5 e.r.) manner under mild conditions. Moreover, it is demonstrated that 2‐Nap‐Q‐1‐M can serve as an efficient diene for a side asymmetric Diels–Alder (D‐A) reaction. This principle can provide a straightforward access to hydrophenalene in an optically active form, which represents a structural core of various natural products and bioactive molecules.

show abstract

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

Cited by 61 publications

References 56 publications

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

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

Enantioselective access to tricyclic tetrahydropyran derivatives by a remote hydrogen bonding mediated intramolecular IEDHDA reaction

Allylsilane Reagent‐Controlled Divergent Asymmetric Catalytic Reactions of 2‐Naphthoquinone‐1‐methide

Contact Info

Product

Resources

About