Bis(alk-2-enyl)zink aus organomagnesiumhalogeniden

Lehmkuhl, Herbert; Döring, Ingo; McLane, Raymond; Nehl, Hans

doi:10.1016/s0022-328x(00)81022-0

Cited by 27 publications

(12 citation statements)

References 8 publications

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“…Bis(allyl)zinc63 is a valuable alternative to allyl‐Grignard reagents in organic synthesis, as it shows distinct selectivities in some cases 63b. 64 The allyl ligands of the sublimable compound were believed to show η 3 bonding in the solid state, until recent single‐crystal X‐ray analysis revealed a μ 2 ‐η 1 :η 1 coordination mode (Figure 6 a).…”

Section: Trends In the Periodic System Of The Elementsmentioning

confidence: 99%

“…The main degradation pathway at elevated temperatures of ≥100 °C is radical coupling of allyl ligands with concomitant formation of Zn 0 70. 71 At lower temperatures of 30 °C to 50 °C, bis(allyl)zinc undergoes an oligomerization in a metallo‐ene reaction 63b. This type of reaction was studied in detail for the allylzinc monocation69 (see Section 5.3.2).…”

Section: Trends In the Periodic System Of The Elementsmentioning

confidence: 99%

“…It was first reported as a side reaction preventing the isolation of [Be(C 3 H 5 ) 2 ] and [Al(C 3 H 5 ) 3 ] 48. Metallo‐ene reactions of neutral [Zn(C 3 H 5 ) 2 ] (“organometallic oligomerization”) were investigated in some more detail by analysis of the organic compounds that were obtained after quenching with electrophiles 63b. 71 The CC bond formation always takes place between the β‐ and the γ‐carbon atom; the opposite regioselectivity (bond formation between C β and C α ) is not observed.…”

Section: Allyl‐specific Reactivitiesmentioning

confidence: 99%

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Structurally Defined Allyl Compounds of Main Group Metals: Coordination and Reactivity

Lichtenberg

Okuda

2013

Angew Chem Int Ed

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Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

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Section: Trends In the Periodic System Of The Elementsmentioning

confidence: 99%

Section: Trends In the Periodic System Of The Elementsmentioning

confidence: 99%

Section: Allyl‐specific Reactivitiesmentioning

confidence: 99%

See 1 more Smart Citation

Structurally Defined Allyl Compounds of Main Group Metals: Coordination and Reactivity

Lichtenberg

Okuda

2013

Angew Chem Int Ed

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“…Bis(allyl)zink63 bietet in der organischen Synthese eine wertvolle Alternative zu Allyl‐Grignard‐Reagentien, da es in einigen Fällen divergierende Selektivitäten zeigt 63b. 64 Für die sublimierbare Verbindung wurde lange eine η 3 ‐Koordination der Allylliganden im Festkörper angenommen, bis Einkristallstrukturanalysen jüngst einen μ 2 ‐η 1 :η 1 ‐Bindungsmodus offenbarten (Abbildung 6 a).…”

Section: Trends Im Periodensystem Der Elementeunclassified

Strukturell definierte Allylverbindungen der Hauptgruppenmetalle: Koordination und Reaktivität

Lichtenberg

Okuda

2013

Angewandte Chemie

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Metallorganische Allylverbindungen sind von Bedeutung als Allylierungsreagentien in der organischen Synthese, als Polymerisationskatalysatoren und als flüchtige Metallvorstufen in den Materialwissenschaften. Während die Allylchemie der Lanthanoide und syntheserelevanter Übergangsmetalle wie Palladium gut etabliert ist, bestand für die Allylchemie der Hauptgruppenmetalle Nachholbedarf. Jüngste Erkenntnisse über die Allylkomplexe der Gruppen 1, 2 und 12–16 zeichnen nun ein vollständigeres Bild. Dies beruht auf dem grundlegenden Verständnis der Metall‐Allyl‐Bindungswechselwirkungen im Festkörper und in Lösung. Außerdem wurden Reaktivitätstrends rational erklärt und neue, allylspezifische Reaktivitätsmuster aufgedeckt. Schlüsselerkenntnisse umfassen 1) die Nutzung unterschiedlicher Metall‐Allyl‐Wechselwirkungen (stark ionisch bis vorwiegend kovalent), 2) das Nutzen synergetischer Effekte in Heterodimetallverbindungen und 3) die Regulierung der Lewis‐Acidität durch Variation der Ladung von Allylkomplexen.

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“…Next, the transfer of different alkyl groups was investigated with freshly prepared zinc organyl compounds (Table 3). ZnMe 2 (3v), Zn(nBu) 2 (3w), [25] Zn(allyl) 2 [26] (2d), and even abulky secondary zinc organyl compound (2c) [25,27] reacted efficiently.N ol imitation was encountered upon switching to aryl based organometallics (2e). [25] Organozinc halides, [24,28] which are generally considered less reactive,also readily gave the desired products 2b, 3x, 3y,a nd 2f.F or aniline derivatives with branched alkyl moieties and allyl groups,the acetylating work-up proved inefficient.…”

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confidence: 99%

Electrophilic Amination with Nitroarenes

2017

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An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with at wostep partial reduction of the nitro group to anitrenoid, whichis used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air-a nd moisture-sensitive aminoboranes were reacted with arange of electrophiles.The method not only represents ad irect transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.

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Bis(alk-2-enyl)zink aus organomagnesiumhalogeniden

Cited by 27 publications

References 8 publications

Structurally Defined Allyl Compounds of Main Group Metals: Coordination and Reactivity

Structurally Defined Allyl Compounds of Main Group Metals: Coordination and Reactivity

Strukturell definierte Allylverbindungen der Hauptgruppenmetalle: Koordination und Reaktivität

Electrophilic Amination with Nitroarenes

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