Phosphine-catalyzed (3+2)/(2+3) sequential annulation involving a triple nucleophilic addition reaction of γ-vinyl allenoates

Feng, Jiaxu; Huang, You

doi:10.1039/c9cc07346a

Cited by 28 publications

(4 citation statements)

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“…Many important skeletons or potentially useful compounds in drug discovery have been synthesized by these methods [5] . Especially, intermolecular or intramolecular cycloaddition reactions using vinylallenes, such as [4+1], [1a–f] [4+2], [1g–m] [4+4], [1n] [4+4+1], [1o] and [3+2]/[2+3] [1p] cycloadditions, developed, respectively by Siegel et al., Murakami et al., and Lee and co‐workers, have become powerful methods to synthesize various ring compounds (Scheme 1 a). It is interesting to note that all these ring formation reactions (except one in Scheme 1 b, see below) using vinylallenes cannot be used to synthesize seven‐membered rings.…”

Section: Methodsmentioning

confidence: 99%

Rhodium(I)‐Catalyzed Three‐Component [4+2+1] Cycloaddition of Two Vinylallenes and CO

Tian

2021

Chemistry A European J

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Transition metal-catalyzed [4+ +2+ +1] reactions of dienes (or diene derivatives such as vinylallenes), alkynes/ alkenes, and CO (or carbenes)a re expected to be the most straightforward approacht os ynthesize challenging seven-membered ring compounds, but so far only limited successes have been realized. Here, an unexpected threecomponent [4+ +2+ +1] reactionb etweent wo vinylallenes and CO was discovered to give highlyf unctionalized tropone derivatives under mild conditions, where one vinylallene acts as aC 4 synthon, the other vinylallene as aC 2 synthon, and CO as aC 1 synthon. It was proposed that this reaction occurred via oxidative cyclization of the diene part of one vinylallene molecule, followed by insertion of the terminal alkene part of the allene moiety in another vinylallene, intot he RhÀCb ond of five-membered rhodacycle. Then, CO insertion andr eductivee limination gave the [4+ +2+ +1] cycloadduct. Further experimental exploration of why ene/yne-vinylallenes and CO gave monocyclic tropone derivatives insteado f6 /7-bicyclic ring products were reported here. Scheme1.Vinylallenes in cycloaddition reactionsand an ew development.

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Section: Methodsmentioning

confidence: 99%

Rhodium(I)‐Catalyzed Three‐Component [4+2+1] Cycloaddition of Two Vinylallenes and CO

Tian

2021

Chemistry A European J

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“…1A). 4 While related annulations of other C3-, C4-, and higher synthons have received attention, [5][6][7] C2-phosphonium 4 has been largely overlooked. Most commonly this species is accessed from ynoate 5 and allows a-umpolung couplings 8 or Michael additions 9,10 with to the best of our knowledge, cycloadditions only reported on two occasions (Fig.…”

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confidence: 99%

Enantioselective synthesis of cyclopentenes by (2 + 3) cycloaddition via a 2-carbon phosphonium

Seitz,

Maddigan-Wyatt,

Cao

et al. 2024

Preprint

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Herein we report a catalytic enantioselective (2 + 3) cycloaddition in which a vinyl phosphonium intermediate serves as the 2-carbon component. The reaction involves an umpolung umpolung coupling sequence enabled by haloacrylates and chiral enantioenriched phosphepine catalysts. The reaction shows good generality providing access to an array of cyclopentenes, with mechanistic studies supporting stereospecific formation of the vinyl phosphonium intermediate which then undergoes annulation with turn over limiting catalyst elimination. Beyond defining a new approach to cyclopentenes these studies demonstrate that haloacrylates can replace ynoates in reaction designs that require exclusive umpolung coupling at both carbons

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“…1 However, the explosive development of phosphine catalysis has been greatly impeded in the past two years most likely due to the "oldpatterned" reaction modes and synthons. 2 Our group has been dedicated to the exploration of phosphine catalysis, aiming at not only valuable skeletons formed in new reactions 3 but also the discovery of brand-new allenoates 4 that may act as totally different building blocks and lead to novel reaction modes, which, in our opinion, may reveal a promising breakthrough for the development of phosphine catalysis in the future.…”

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confidence: 99%

Phosphine-Catalyzed Sequential [3+3]/Aza-6π-Electrocyclization Reaction of Cross-Conjugated Azatrienes and δ-Sulfonamido-Allenoates

Huang

2020

Org. Lett.

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An unprecedented sequential [3+3]/aza-6π-electrocyclization between cross-conjugated azatrienes and δ-sulfonamido-allenoates, catalyzed by phosphine, has been developed, which provides efficient and facile access to highly functionalized tetrahydroisoquinoline derivatives. The products can be easily transformed into (dihydro)isoquinolines and their fused polycyclic compounds. The reactivity of both azatrienes and δ-sulfonamido-allenoates in this text, acting as a five-atom unit, is unique in the phosphine-catalyzed annulations of allenoates.

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Phosphine-catalyzed (3+2)/(2+3) sequential annulation involving a triple nucleophilic addition reaction of γ-vinyl allenoates

Abstract: A phosphine-catalyzed (3+2)/(2+3) sequential annulation involving a triple nucleophilic addition reaction of γ-vinyl allenoates was successfully developed.

Cited by 28 publications

References 81 publications

Rhodium(I)‐Catalyzed Three‐Component [4+2+1] Cycloaddition of Two Vinylallenes and CO

Rhodium(I)‐Catalyzed Three‐Component [4+2+1] Cycloaddition of Two Vinylallenes and CO

Enantioselective synthesis of cyclopentenes by (2 + 3) cycloaddition via a 2-carbon phosphonium

Phosphine-Catalyzed Sequential [3+3]/Aza-6π-Electrocyclization Reaction of Cross-Conjugated Azatrienes and δ-Sulfonamido-Allenoates

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