Two-directional carbon chain elongation via the consecutive 1,4-addition of allyl malononitrile and the Cope rearrangement on an alkynoate platform

Kamijo, Shunsuke; Kamijo, Kaori; Magarifuchi, Daiki; Ozawa, Ryota; Tao, Katsumi; Murafuji, Toshihiro

doi:10.1016/j.tetlet.2015.11.081

Cited by 5 publications

(2 citation statements)

References 37 publications

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“…Murafuji and co-workers developed a method for two-directional carbon chain elongation through phosphine-catalyzed reactions of allyl malononitrile with alkynoates (Scheme 402). 469 Allyl malononitrile and a diverse array of substituted alkynoates were treated with PCy 3 (20 mol %) and then heated under microwave irradiation at 180 °C for 1 h. The corresponding dienes presenting various substituents were obtained in moderate to good yields.…”

Section: Nucleophilic Phosphine Catalysis Of Acetylenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Nucleophilic Phosphine Catalysis Of Acetylenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…The treatment of 4y with benzylamine allows a smooth generation of pyrrolidin-2-one product 7a in 73% yield, 17 and the m-CPBA-mediated epoxidation selectively occurred on the more electron-rich double bond to deliver product 8a in 71% yield. 18 In addition, while the present reaction is not applicable to γ-substituted allenoates, the Giese reaction, to some extent, provides a pathway by enabling an expedient introduction of either aryl or alkyl groups to the γ-position (9a, 10a). 19,20 Finally, hepta-2,6dienoate product 11a could be readily obtained through Cope rearrangement from 4y.…”

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confidence: 92%

Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates

et al. 2019

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A strategically novel Pd-catalyzed nucleophilic addition induced allylic alkylation reaction (NAAA) of allenoates has been successfully accomplished. By judiciously integrating ZnCl 2 -promoted Michael addition with Pd-catalyzed allylic alkylation, allenoates readily undergo allyl-sunfonylation at the internal double bond, thus providing a straightforward avenue for the rapid assembly of a host of structurally diversified α-allyl-β-sufonylbut-3-enoate derivatives. The success of this transformation profits from a delicate control of the reaction kinetic of each elementary step, thanks to the synergistic interaction of Pd/Zn bimetallic system, thus suppressing either direct allylic sulfonylation or premature quenching of therein in situ generated ester enolate intermediate. Furthermore, by expanding the scope of workable Michael acceptor beyond those previously required doubly activated ones, such as methylenemalononitrile, the present work substantially enriches the repertoire of NAAA reactions.

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Molecular Rearrangements

Coxon¹

2020

Organic Reaction Mechanisms · 2016

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Two-directional carbon chain elongation via the consecutive 1,4-addition of allyl malononitrile and the Cope rearrangement on an alkynoate platform

Cited by 5 publications

References 37 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates

Molecular Rearrangements

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