Asymmetric Synthesis of [2.2.2]-Bicyclic Lactones via All-Carbon Inverse-Electron-Demand Diels–Alder Reaction

Saktura, Maciej; Grzelak, Paulina; Dybowska, Joanna; Albrecht, Łukasz

doi:10.1021/acs.orglett.0c00138

Cited by 16 publications

(10 citation statements)

References 72 publications

(18 reference statements)

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“…It should be noted that the use of 3,3-disubstituted enals is essential to the isolation of desired products.L ater,asimilar strategy using 2,3-disubstituted a,bunsaturated aldehydes 199 as dienophiles was developedb y Albrechta nd co-workers (Scheme 52 b). [74] However, the resulting bicyclic lactones 201 were not stable enoughf or purification. Further transformation of the cycloadducts 201 via Wittig reactionino ne pot allowed to isolate anumber of correspond-ing a,b-unsaturated esters 202 in good yields together with excellentdiastereo-and enantioselectivities.…”

Section: Enantioselective Iedda Reactions Of 2-pyronesmentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

Huang

Kouklovsky

Torre

2021

Chemistry A European J

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Inverse‐electron‐demand Diels–Alder (IEDDA) reactions of electron‐poor 2‐pyrones as electrophilic dienes have been extensively studied in the past fifty years. These reactions provide an efficient access to bridged bicyclic lactones and their derivatives, such as densely functionalized 1,3‐cyclohexadienes after CO2 extrusion and polysubstituted aromatic compounds through elimination. This reaction has been used for the synthesis of many biologically active natural products and drug candidates. In this review, the developments of these IEDDA reactions including non‐catalytic, Lewis acid‐catalyzed and organocatalytic IEDDA reactions, and their applications in total synthesis are discussed in detail.

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Section: Enantioselective Iedda Reactions Of 2-pyronesmentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

Huang

Kouklovsky

Torre

2021

Chemistry A European J

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“…[97] Another strategy for asymmetric IEDDA cycloadditions was recently reported in close succession by the groups of Snyder [98] and Albrecht. [99] The Lewis acid-catalyzed asymmetric IEDDA reaction of 2pyrones have been successfully developed with various metals utilizing TADDOL or BINOL as chiral promoters. [100,101] A recent Scheme 47.…”

Section: [4 + 2]-cycloadditionmentioning

confidence: 99%

“…Asymmetric IEDDA cycloadditions of coumalate 191. [98,99] example that allowed the short synthesis of the bioactive natural product (+)-MK7607 (259) started with the ytterbiumcatalyzed activation of pyrones 255 with 2,2-dimethyl-1,3dioxole (256) (Scheme 51). [102] By coordination to both carbonyls of pyrone 255, the chiral catalyst is forcing the alkene 256 to a stereoselective cycloaddition due to steric shielding.…”

Section: [4 + 2]-cycloadditionmentioning

confidence: 99%

2‐Pyrone – A Privileged Heterocycle and Widespread Motif in Nature

et al. 2021

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In memory of Klaus HafnerThe 2-pyrone moiety can be found in a large number of natural products with a wide range of biological activities, including antibiotic, antifungal, cytotoxic, neurotoxic, phytotoxic, antiinflammatory and cardiotonic effects. With its heterocyclic structure encompassing the chemical nature of conjugated dienes, lactones, Michael acceptors and arenes, it can undergo a great variety of transformations such as cycloadditions, ringopening reactions, cross-couplings and lactamizations. Thus, 2-pyrones represent valuable synthetic precursors and worthwhile targets in organic, polymer, and medical chemistry. Owing to its exquisite chemical and physical properties, the synthesis and further transformations of 2-pyrones have attracted considerable attention over the past decade, showcasing transition metal and metal free strategies and using readily available starting materials, notably those stemming from renewable resources.

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“…10 Recently, we have developed a new strategy for the synthesis of bicyclo[2.2.2]lactones (Scheme 1, top panel). 11 It was based on dienamine-mediated [4+2] cycloaddition between ,-unsaturated aldehydes and corresponding coumalates. In continuation of our efforts towards the development of vinylogous organocatalytic synthetic strategies leading to bicyclic compounds, we turned our attention to 1,3,6-trimethyl-5-formyluracil (1) (Scheme 1, bottom panel).…”

Section: Feature Synthesismentioning

confidence: 99%

Aminocatalytic Synthesis of Uracil Derivatives Bearing a Bicyclo[2.2.2]octane Scaffold via a Doubly Cycloadditive Reaction Cascade

Saktura¹,

Frankowski²,

Joachim³

et al. 2020

Synthesis

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Aminocatalytic synthesis of highly enantiomerically enriched uracil derivatives bearing a bicyclo[2.2.2]octane scaffold is described. The developed strategy utilizes 1,3,6-trimethyl-5-formyluracil and α,β-unsaturated aldehydes as starting materials and has been realized employing various aminocatalytic activation strategies operating in a synergistic manner. The reaction cascade can be described as doubly cycloadditive as it consists of two consecutive Diels–Alder cycloadditions allowing for a facile construction of the bicyclo[2.2.2]octane scaffold. Notably, both steps proceed with dearomatization of the partially aromatic uracil moiety. Excellent stereoselectivity of the reaction cascade is ensured by the use of 2-(diphenylmethyl)pyrrolidine as aminocatalyst.

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Asymmetric Synthesis of [2.2.2]-Bicyclic Lactones via All-Carbon Inverse-Electron-Demand Diels–Alder Reaction

Cited by 16 publications

References 72 publications

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

2‐Pyrone – A Privileged Heterocycle and Widespread Motif in Nature

Aminocatalytic Synthesis of Uracil Derivatives Bearing a Bicyclo[2.2.2]octane Scaffold via a Doubly Cycloadditive Reaction Cascade

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