Reductive coupling of ferrocenyl atones by low-valent titanium reagents. Synthesis and characterization of some 1,2-diferrocenylethenes and 1,2-diferrocenylethanes

Dang, Y.; Geise, H. J.; Dommisse, Roger; Esmans, Eddy L.

doi:10.1016/s0020-1693(00)83205-3

Cited by 12 publications

(3 citation statements)

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“…These modified McMurry reaction conditions have proved essential for the synthesis of tetraferrocenylethylene and are applicable in this case also, affording 2 in 23% yield (after chromatographic separation of the corresponding byproduct 1,2-diferrocenyl-1,2-diphenylethane) as an air-stable orange powder. Although 2 is a known compound and by definition not a cumulenealthough it may formally be considered a [1]cumuleneit is the logical starting member in our family of Fc(C 6 H 5 )C x (C 6 H 5 )Fc compounds ( x = 2, 3, 4, 5, 6, 7). In solution, NMR spectroscopy indicates formation of the trans-anti isomer only (compare Chart ), which may be rationalized by minimization of steric repulsions in this “as-short-as-possible” pseudo-cumulene.…”

Section: Resultsmentioning

confidence: 99%

α,ω-Diferrocenyl Cumulene Molecular Wires. Synthesis, Spectroscopy, Structure, and Electrochemistry

et al. 2004

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Cumulene sp-carbon molecular wires C 2 [Fc(Ph)CdC(Ph)Fc] up to C 7 [Fc(Ph)CdCdCd CdCdCdC(Ph)Fc] endcapped by two electroactive ferrocenyl groups are presented in this report. Synthetically, ferrocenyl cumulenes can be built-up by a modular strategy using C 1 synthon ferrocenyl(phenyl)ketone as starting material with various acetylenic/propargylic/ homopropargylic C 2 -C 5 reagents, taking into account and exploiting the efficient stabilization of an electron-deficient carbenium center by an adjacent ferrocenyl moiety. With increasing cumulene chain length the reactivity of cumulenes increases considerably, indicating steric protection as the main requirement for bulk stability. Even cumulenes C 2 , C 4 , and C 6 are conjugated "molecular wires" effecting electronic communication between the terminal ferrocenyl substituents, whereas odd cumulenes C 3 , C 5 , and C 7 are nonconjugated and electronically decoupled due to their orthogonal terminal π-systems. Electrochemically, separate redox waves can be detected up to a C 6 cumulene spacer, but the electronic communication between the endcapping redox-active ferrocenyl substituents decreases with increasing cumulene length.

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Section: Resultsmentioning

confidence: 99%

α,ω-Diferrocenyl Cumulene Molecular Wires. Synthesis, Spectroscopy, Structure, and Electrochemistry

et al. 2004

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“…On the other hand, dimethyl (Z)-2,3-diferrocenylbut-2-enedioate displays interesting redox and solvatochromic properties (Solntsev et al, 2011). As typical procedures for the preparation of tetrasubstituted ethenes containing a ferrocenyl substituent, conversions of the corresponding ketones under the McMurry reaction conditions (Top et al, 1997) or reductive coupling using low-valent titanium agents are recommended (Dang et al, 1990). In both cases, the reported yields are satisfactory to good, but a serious disadvantage is the formation of side-products.…”

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“…Here we report the analogous synthesis and crystal structure of the known title compound, (E)-1, with m.p. 485-487 K. For the previously described synthesis of this product (Dang et al, 1990), a m.p. of 489-491 K and a yield of 17% were reported and the authors tentatively assigned the (E)-configuration to the obtained compound.…”

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Crystal structure of (E)-1,2-diferrocenyl-1,2-bis(furan-2-yl)ethene

et al. 2018

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The McMurry Coupling and Related Reactions

Takeda

Tsubouchi

2013

Organic Reactions

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The McMurry coupling reaction has been recognized as one of the most efficient methods for the synthesis of alkenes from carbonyl compounds. This reaction can be applied to the preparation of various alkenes that are otherwise difficult to prepare. For example, sterically congested tetrasubstituted alkenes as well as medium to large membered rings involving natural products may be accessed via this process. This coupling utilizes various low‐valent titanium reagents generated by the reduction of titanium (III or IV) chloride with K, Zn, LiAlH 4 , C 8 K, amongst others. Furthermore, a variety of low‐valent metal species other than titanium, including aluminum, zirconium, niobium, molybdenum, indium, tungsten, and samarium, have also been found to promote the reductive coupling of carbonyl compounds. The scope and limitations of these reagent systems are reviewed in this chapter, together with the stereochemistry and reaction mechanism. This reaction is categorized into four coupling modes: i) homocoupling giving symmetrical alkenes, ii) mixed coupling giving unsymmetrical alkenes, iii) intramolecular coupling giving cycloalkenes, and iv) tandem coupling giving cyclic polyenes. Characteristics of these reaction modes are described briefly. A selection of synthetic applications are reviewed, including examples of the preparation of sterically congested and strained alkenes, medium to large‐ring compounds, biologically active targets, as well as substrates applicable in material science. Experimental conditions used for this versatile process are summarized to assist the choice of suitable conditions.

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Reductive coupling of ferrocenyl atones by low-valent titanium reagents. Synthesis and characterization of some 1,2-diferrocenylethenes and 1,2-diferrocenylethanes

Cited by 12 publications

References 21 publications

α,ω-Diferrocenyl Cumulene Molecular Wires. Synthesis, Spectroscopy, Structure, and Electrochemistry

α,ω-Diferrocenyl Cumulene Molecular Wires. Synthesis, Spectroscopy, Structure, and Electrochemistry

Crystal structure of (E)-1,2-diferrocenyl-1,2-bis(furan-2-yl)ethene

The McMurry Coupling and Related Reactions

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