Metal‐Catalyzed Hydroalumination Reactions

Dahlmann, Marc; Lautens, Mark

doi:10.1002/3527600159.ch2

Cited by 7 publications

(5 citation statements)

References 61 publications

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“…We have shown that Zr(O t Bu) 3 @SiO 2 /Al 2 O 3 -catalyzed C–H bond alumination is effective for derivatizing sp 3 -hybridized C–H bonds in hydrocarbon chains, ranging in size all the way from large macromolecules to methane. The formation of alkylaluminum species as the primary products allows for versatile subsequent transformations, such as the oxygenation with O 2 employed here, as well as carboxylation with CO 2 or halogenation with I 2 , catalytic chain growth in the presence of olefins, or organometal-catalyzed cross-coupling . The earth-abundant, inexpensive, and readily available alkoxyzirconium molecular precatalyst and triethylaluminum reagent further add to the benefits of this new transformation.…”

Section: Discussionmentioning

confidence: 94%

“…The formation of alkylalu- minum species as the primary products allows for versatile subsequent transformations, such as the oxygenation with O 2 employed here, as well as carboxylation with CO 2 or halogenation with I 2 , catalytic chain growth in the presence of olefins, or organometal-catalyzed cross-coupling. 48 The earthabundant, inexpensive, and readily available alkoxyzirconium molecular precatalyst and triethylaluminum reagent further add to the benefits of this new transformation. A two-step catalytic sequence is proposed for the dominant pathway (Figure 6), involving hydrocarbon zirconation followed by heterobimetallic alkyl exchange of surface zirconium hydrocarbyl species and ethylaluminum.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane

et al. 2023

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C–H/Et-Al exchange in zirconium-catalyzed reactions of saturated hydrocarbons and AlEt3 affords versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(OtBu)4 on silica/alumina gives monopodal SiO–Zr(OtBu)3 surface pre-catalyst sites that are activated in situ by ligand exchange with AlEt3. The catalytic C–H alumination of dodecane at 150 °C followed by quenching in air affords n-dodecanol as the major product, revealing selectivity for methyl group activation. Shorter hydrocarbon or alcohol products were not detected under these conditions. Catalytic reactions of cyclooctane and AlEt3, however, afford ring-opened products, indicating that C–C bond cleavage occurs readily in methyl group-free reactants. This selectivity for methyl group alumination enables the C–H alumination of polyethylenes, polypropylene, polystyrene, and poly-α-olefin oils without significant chain deconstruction. In addition, the smallest hydrocarbon, methane, undergoes selective mono-alumination under solvent-free catalytic conditions, providing a direct route to Al–Me species.

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Section: Discussionmentioning

confidence: 94%

Section: ■ Conclusionmentioning

confidence: 99%

Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane

et al. 2023

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“…Houk et al 23,24 and others 25 have examined the reaction path for the analogous hydroboration reaction with a variety of substrates. The intermediates and transition structures found in these studies are consistent with those for the hydroalumination pathway described earlier.…”

Section: Introductionmentioning

confidence: 99%

Hydroalumination of Cyclopropane: A Transition State Study

2013

Chem Sci Trans

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Abstract:The hydroalumination of cyclopropane has been investigated using the B3LYP density functional method employing several split-valence basis sets. It is shown that the reaction proceeds via a four-centered transition state. Calculations at higher levels of theory were also performed at the geometries optimized at the B3LYP level, but only slight changes in the barriers were observed. Structural parameters for the transition state are also reported.

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“…First, different catalysts were investigated (Table ). When the catalysts used for other hydroalumination reactions reported in literatures were used in this study, the conversion and regioselectivity were unsatisfied (entries 1–4). Next, we turned to iron as a catalyst.…”

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confidence: 98%

Iron-Catalyzed Alkene Hydroalumination

Zhang

et al. 2023

Org. Lett.

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Hydroalumination of olefins generally gives thermodynamically controlled anti-Markovnikov addition selectivity in literatures. In this paper, a highly Markovnikov hydroalumination of aromatic terminal alkenes was realized to prepare various new benzylaluminum complexes by using the well-defined 2,9-diaryl-1,10-phenanthroline modified iron complex as the catalyst and commercially available DIBAL-H as the aluminum hydride reagent. This is the first ironcatalyzed alkene hydroalumination, and the regioselectivity observed in this study is different from the related reactions reported in the literatures.

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Metal‐Catalyzed Hydroalumination Reactions

Cited by 7 publications

References 61 publications

Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane

Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane

Hydroalumination of Cyclopropane: A Transition State Study

Iron-Catalyzed Alkene Hydroalumination

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