The Intramolecular Allenolate Rauhut–Currier Reaction

MacKay, James A.; Landis, Zachary; Motika, Stephen E.; Kench, Margaret H.

doi:10.1021/jo3015769

Cited by 19 publications

(7 citation statements)

References 41 publications

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“…In 2012, MacKay and co-workers reported the synthesis of functionalized 2-cyanocyclopentenes through the α-addition–Michael addition pathway of enynes (Scheme ). The reactions gave 2-cyanocyclopentenes in good yields from substrates featuring various electron-withdrawing groups (i.e., ester, nitrile, and sulfone).…”

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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“…A plausible mechanism for this new process involving a Michael-type addition and a double cyclization is depicted in Scheme . In this case, the allenylmetallate Ia , resulting from the addition of the propargylmalonate enolate to the Fischer carbene, would undergo an intramolecular 5- exo cyclization by nucleophilic attack over the C–C triple bond to give cyclic metallatriene V (cyclization d) . The latter readily would undergo cyclopentannulation and proton rearrangement to cyclopentadienyl anion intermediate VI (cyclization a), and then protonation would give rise to compounds 6 and 7…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic Addition/Double Cyclization Cascade Processes between Enynyl Fischer Carbene Complexes and Alkynyl Malonates

2014

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Two new selective cascade processes for enynyl Fischer carbene complexes 1 are described in their reaction with alkynyl malonates. When carbene complexes 1 react with the sodium enolate of homopropargyl malonates 3 a consecutive Michael type addition/cyclopentannulation/6-exo cyclization takes place leading, in a regio and stereoselective way, to n/5/6 angular tricyclic compounds 5. Furthermore, when propargylic malonates are used, a delayed protonation of the reaction mixture allows intermediate 1,4addition adduct Ia to evolve through a 5-exo cyclization, consisting in an intramolecular nucleophilic attack from the central carbon of the allenylmetallate over the triple CC bond. Further spontaneous cyclopentannulation of the resulting metallatriene gives rise to bicyclic and linear polycyclic compounds 6 and 7, some of them bearing a polyquinane framework.

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“…In a different and interesting kind of IRC reaction, MacKay et al reported phosphine catalyzed ring closure along with addition of cyanide across alkyne (Scheme 34). 45 Although end product resembles to be result of double Michael addition initiated by CN but reaction doesn't proceed in the absence of phosphine catalyst. In the proposed mechanism initial attack of phosphine across triple bond was followed by ring closure reaction.…”

Section: Irc-fundamental Developmentsmentioning

confidence: 99%