Temperature-Dependent Divergent Cyclopentadiene Synthesis through Cobalt-Catalyzed C–C Activation of Cyclopropenes

Zeng, Tianlong; Li, Ying; Wang, Ruobin; Zhu, Jun

doi:10.1021/acs.orglett.4c00959

Cited by 3 publications

(1 citation statement)

References 31 publications

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“…This is likely due to their high propensity to generate carbene intermediates, which tend to evolve through cyclopropanations and C–H insertions, among other pathways . Indeed, metal-catalyzed (3 + n ) annulations of cyclopropenes are limited to a handful of processes, most of them promoted by precious metals like Rh, Pd, or Ru. , …”

Section: Introductionmentioning

confidence: 99%

Cobalt-Catalyzed (3 + 2) Cycloaddition of Cyclopropene-Tethered Alkynes: Versatile Access to Bicyclic Cyclopentadienyl Systems and Their CpM Complexes

Lázaro-Milla,

da Concepción,

Fernández

et al. 2024

ACS Catal.

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Low-valent cobalt complexes can promote intramolecular (3 + 2) cycloadditions of alkyne-tethered cyclopropenes to provide bicyclic systems containing highly substituted cyclopentadienyl moieties with electronically diverse functional groups. The adducts can be easily transformed into new types of CpRh(III) and CpIr(III) complexes, which show catalytic activity in several relevant transformations. Preliminary computational (DFT) and experimental studies provide relevant information on the mechanistic peculiarities of the cobalt-catalyzed process and allow us to rationalize its advantages over the homologous rhodium-promoted reaction.

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Section: Introductionmentioning

confidence: 99%

Cobalt-Catalyzed (3 + 2) Cycloaddition of Cyclopropene-Tethered Alkynes: Versatile Access to Bicyclic Cyclopentadienyl Systems and Their CpM Complexes

Lázaro-Milla,

da Concepción,

Fernández

et al. 2024

ACS Catal.

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Synthesis of Multisubstituted Cyclopentadiene Derivatives from 3,3-Disubstituted Cyclopropenes and Internal Alkynes Catalyzed by Low-Valent Niobium Complexes

Akiyama,

Kusamoto,

Mashima

et al. 2024

J. Am. Chem. Soc.

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A low-valent niobium species generated from NbCl 5 and 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (Si-Me-CHD) in combination with PPh 3 catalyzed a [2+2+1]-cycloaddition reaction of 3,3-disubstituted cyclopropenes and 2 equiv of diaryl/dialkylalkynes, leading to isomeric mixtures of multisubstituted cyclopentadienes 3−5. The initial catalyst activation process was a one-electron reduction of NbCl 5 with Si-Me-CHD to provide [NbCl 3 (μ-Cl) (L)] 2 (L = PMe 2 Ph ( 6), L = PPh 3 (7)) in the presence of phosphine ligands. An NMR spectroscopic time course experiment using complex 7 as the catalyst revealed an induction period for the product formation, corresponding to an additional one-electron reduction of 7 by the substrates to give catalytically active η 2 -alkyne complexes of NbCl 3 . A combined computational and experimental study clarified the mechanism of this unprecedented [2+2+1]-cyclopentadiene synthesis; a ratedetermining 1,2-insertion of cyclopropene into η 2 -alkyne niobium species to form cyclopropane-fused metallacyclopentene followed by ring-opening β-C elimination provides a dienylalkylidene intermediate prior to incorporation of the second alkyne through carbene/alkyne metathesis. We also demonstrated the synthetic utility of the multisubstituted cyclopentadienes as the cyclopentadienyl ligands by derivatizing to the corresponding lithium cyclopentadienide, which is applicable for the synthesis of ferrocene 10.

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Catalytic haloallylation/Zr-mediated dienyne cyclization/isomerization sequence for tailored cyclopentadiene substitution

Gobin,

Nikšić-Franjić,

Topolovčan

2025

Org. Chem. Front.

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Temperature-Dependent Divergent Cyclopentadiene Synthesis through Cobalt-Catalyzed C–C Activation of Cyclopropenes

Cited by 3 publications

References 31 publications

Cobalt-Catalyzed (3 + 2) Cycloaddition of Cyclopropene-Tethered Alkynes: Versatile Access to Bicyclic Cyclopentadienyl Systems and Their CpM Complexes

Cobalt-Catalyzed (3 + 2) Cycloaddition of Cyclopropene-Tethered Alkynes: Versatile Access to Bicyclic Cyclopentadienyl Systems and Their CpM Complexes

Synthesis of Multisubstituted Cyclopentadiene Derivatives from 3,3-Disubstituted Cyclopropenes and Internal Alkynes Catalyzed by Low-Valent Niobium Complexes

Catalytic haloallylation/Zr-mediated dienyne cyclization/isomerization sequence for tailored cyclopentadiene substitution

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