Conversion of (vinylketene)tricarbonyliron(0) complexes to (vinylketenimine)tricarbonyliron(0) complexes

Richards, Christopher J.; Thomas, Susan E.

doi:10.1039/c39900000307

Cited by 23 publications

(6 citation statements)

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“…For instance, tricarbonyliron(0) complexes of α,β-unsaturated ketones react with alkylithium reagents under an atmosphere of nitrogen to afford 1,4-diketones, while under an atmosphere of carbon monoxide, tricarbonyl(η 4 -vinylketene)iron(0) complexes are generated in good yield . Thomas and co-workers have used these iron(0)vinylketene complexes to synthesise a number of important organic products, including phenols, cyclopentadienones, cyclopropanes, β,γ-unsaturated carbonyl compounds, and vinylketeneimines …”

Section: Introductionmentioning

confidence: 99%

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

et al. 1997

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The binuclear allenyl complex [Fe2(CO)6(μ-PPh2){μ-η1:η2 α,β-(H)CαCβCγH2}] (1) has been prepared, and its reactivity with organolithium nucleophiles is described. Prop-2-yne bromide reacts with [Fe2(CO)7(μ-PPh2)]-Na+, via an SN2 mechanism, to give [Fe2(CO)6(μ-PPh2){μ-η1:η2 α,β-(H)CαCβCγH2}], the first example of a phosphido-bridged allenyl complex. The molecular structure of [Fe2(CO)6(μ-PPh2){μ-η1:η2-(H)CαCβCγH2}] (1) was determined by single-crystal X-ray diffraction and shows that the allenyl ligand is coordinated through Cα−Cβ. Variable-temperature 1H and 13C NMR studies reveal a high-energy exchange process that equilibrates the diastereotopic allenyl protons, presumably via a zwitterionic intermediate, as well as two independent trigonal rotations that act to exchange the carbonyl ligands on each unique Fe(CO)3 group. Complex 1 reacts with organolithium reagents (RLi; R = Me, nBu, Ph, C4H3S), via allenyl−carbonyl−nucleophile coupling, to afford the binuclear β,γ-unsaturated ketones [Fe2(CO)5{P(OMe)3}(μ-PPh2)(μ-η1:η2-{RC(O)CH2}CCH2)] (R = Me, 3a; nBu, 3b; Ph, 3c; C4H3S, 3d), and a single-crystal X-ray structure determination of 3a was undertaken to confirm the connectivity of the hydrocarbyl ligand. The most likely mechanism for the formation of 3a − d involves nucleophilic attack of R- at CO to give an acylate intermediate followed by migration of RCO to Cα of the allenyl and protonation of the resulting enolate to give the unstable alkenyl complexes [Fe2(CO)5(μ-PPh2)(μ-η1(C):η1(C):η2(C)-{RC(O)CH2}CCH2)] (R = Me, 2a; Bu, 2b; Ph, 2c; C4H3S, 2d). Finally, substitution of the metal-coordinated ester carbonyl in 2a − d with trimethylphosphite affords 3a − d as stable crystalline products.

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Section: Introductionmentioning

confidence: 99%

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

et al. 1997

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“…Interest in metal-bound vinylketenes as reaction intermediates [ 1013 – 1015 ] led to facile preparation of (vinylketene)tricarbonyliron(O) complexes [ 1016 ], and the synthesis of (vinylketeneimine)tricarbonyliron(O) complexes [ 1017 ].…”

Section: Addendamentioning

confidence: 99%

New chemical and stereochemical applications of organoiron complexes

Fatiadi

1991

J. RES. NATL. INST. STAN.

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The objective of this review is to provide a current overview of the rapidly developing chemistry of organometallic complexes and particularly organoiron complexes useful in asymmetric and stereoselective reactions. Also covered are stereoselective reactions of α, β-unsaturated acyl ligands bound to the chiral auxiliary [(η5-C5H5) Fe(CO)(PPh3)] and new applications of organoiron complexes in the synthesis of natural products. The mechanistic aspects and stabilizing effects of the Fe(CO)3 group for alkenes or conjugated dienes are discussed. A brief summary of recent work on the special role of iron in biological reactions is also included.

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“…Additionally, the iron complexes of vinylketenes exhibit noteworthy synthetic transformations. , For example, electron-deficient alkynes add to the vinylketene complexes via insertion to yield stable 1:1 adducts (eq ). However, the particulars of the reactivity of η 4 -(vinylketenimine)iron complexes, , which are easily prepared from the corresponding (vinylketene)iron complexes, are largely unknown. On the basis of η 4 -(vinylketene)iron complexes reactivity (eq ), we envisaged that (vinylketenimine)iron complexes could be converted into η 3 -allyl iron complexes through alkyne insertion.…”

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confidence: 99%

Pyrrole Formation via Reactivity of η⁴-(Vinylketenimine)iron Complexes with Electron-Deficient Alkynes

et al. 2021

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When electron-deficient alkynes reacted with η 4 -(vinylketenimine)iron complexes, pyrroles were produced. Pyrrole formation involved the [2 + 3] cycloaddition of alkyne to the ketenimine moiety, migration of the vinyl group, and decomplexation. Either alkynes bearing two electron-withdrawing groups, or terminal alkynes with an electron-withdrawing group reacted to generate pyrroles. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.1c00321.Experimental details; 1 H NMR and 13 C NMR spectra; X-ray crystallographic data for 4a and 2l (PDF)Accession CodesCCDC 2074661 and 2074664 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

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Conversion of (vinylketene)tricarbonyliron(0) complexes to (vinylketenimine)tricarbonyliron(0) complexes

Abstract: Heating (vinylketene)tricarbonyliron(O) complexes with isonitriles a t 80 "C gives (vinylketenimine)tricarbonyliron(O) complexes via intermediate (vinylketene)dicarbonylisonitrileiron(O) complexes.

Cited by 23 publications

References 3 publications

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

New chemical and stereochemical applications of organoiron complexes

Pyrrole Formation via Reactivity of η⁴-(Vinylketenimine)iron Complexes with Electron-Deficient Alkynes

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Conversion of (vinylketene)tricarbonyliron(0) complexes to (vinylketenimine)tricarbonyliron(0) complexes

Abstract: Heating (vinylketene)tricarbonyliron(O) complexes with isonitriles a t 80 "C gives (vinylketenimine)tricarbonyliron(O) complexes via intermediate (vinylketene)dicarbonylisonitrileiron(O) complexes.

Cited by 23 publications

References 3 publications

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe2(CO)6(μ-PPh2){μ-η1:η2α,β-(H)CαCβCγH2}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe2(CO)6(μ-PPh2){μ-η1:η2α,β-(H)CαCβCγH2}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

New chemical and stereochemical applications of organoiron complexes

Pyrrole Formation via Reactivity of η4-(Vinylketenimine)iron Complexes with Electron-Deficient Alkynes

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Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe₂(CO)₆(μ-PPh₂){μ-η¹:η²_α,β-(H)C_αC_βC_γH₂}]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

Pyrrole Formation via Reactivity of η⁴-(Vinylketenimine)iron Complexes with Electron-Deficient Alkynes