Functional group reductions with Lewis base adducts of gallane

Raston, Colin L.; Siu, A. F. H.; Tranter, Carolyn J.; Young, David J.

doi:10.1016/s0040-4039(00)78218-9

Cited by 38 publications

(19 citation statements)

References 14 publications

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“…The Lewis acid‐base adduct 1 c does not show a marked conversion increase when additional donor is added (Table 1). This might be due to the fact that Me 3 N⋅GaH 3 ( 1 c ) is a mild reducing agent, which for example, selectively reduces the carbonyl group in 4‐bromophenylacyl bromide, but not the C−Br bond . Therefore, 1 c was not applied in further HDF studies.…”

Section: Resultsmentioning

confidence: 99%

“…This might be due to the fact that Me 3 N·GaH 3 (1c)i samild reducing agent, which for example, selectively reduces the carbonyl group in 4-bromophenylacyl bromide, but not the CÀBr bond. [6] Therefore, 1c was not appliedi nf urther HDF studies. The best results for the catalytic HDF of 3 with 1a could be obtained with 30 mol %t riethylamine and for 1b with 10 mol %d iglyme added to the toluene mixture.T hese conditions were appliedf or the subsequentHDF reactions.…”

Section: Resultsmentioning

confidence: 99%

“…The less polarized Ga−H bond results in a weaker Lewis acidity of gallanes, which usually leads to a lower reactivity compared to alanes . However, earlier studies showed that gallane complexes are milder and more selective reducing agents than similar alane complexes and exhibit a higher selectivity in hydrogallation reactions than the corresponding alanes in hydroalumination reactions . For example, the hydroalumination of 1,4‐bis(trimethylsilylethynyl)benzene with di( tert ‐butyl)aluminum hydride yields the cis ‐product, which slowly isomerizes at elevated temperatures to the thermodynamically favored trans ‐product .…”

Section: Introductionmentioning

confidence: 99%

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Gallium Hydrides and O/N‐Donors as Tunable Systems in C−F Bond Activation

Jaeger

Walter

Ehm

et al. 2018

Chemistry An Asian Journal

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The gallium hydrides (iBu) GaH (1 a), LiGaH (1 b) and Me N⋅GaH (1 c) hydrodefluorinate vinylic and aromatic C-F bonds when O and N donor molecules are present. 1 b exhibits the highest reactivity. Quantitative conversion to the hydrodefluorination (HDF) products could be observed for hexafluoropropene and 1,1,3,3,3-pentafluoropropene, 94 % conversion of pentafluoropyridine and 49 % of octafluorotoluene. Whereas for the HDF with 1 b high conversions are observed when catalytic amounts of O donor molecules are added, for 1 a, the addition of N donor molecules lead to higher conversions. The E/Z selectivity of the HDF of 1,1,3,3,3-pentafluoropropene is donor-dependent. DFT studies show that HDF proceeds in this case via the gallium hydride dimer-donor species and a hydrometallation/elimination sequence. Selectivities are sensitive to the choice of donor, as the right donor can lead to an on/off switching during catalysis, that is, the hydrometallation step is accelerated by the presence of a donor, but the donor dissociates prior to elimination, allowing the inherently more selective donorless gallium systems to determine the selectivity.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Gallium Hydrides and O/N‐Donors as Tunable Systems in C−F Bond Activation

Jaeger

Walter

Ehm

et al. 2018

Chemistry An Asian Journal

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“…Finally, it is noteworthy that Lewis base adducts of gallane (LGaH 3 ) reduce cyclic ketones, enones and˛-haloketones to the corresponding alcohols in excellent yields 254 . These reagents show some promise as a new extension of the boron-type reductions of carbonyl compounds.…”

Section: Using Boron-containing Reagentsmentioning

confidence: 99%

Some Synthetic Uses of Double‐Bonded Functional Groups

Hoyle

2009

Patai's Chemistry of Functional Groups

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“…Neben dem ¹klassischenª Einsatzgebiet der Alane als selektive Reduktionsmittel in der organischen Synthese [3] finden ihre leicht flu È chtigen Lewis-Basen-Addukte vermehrt Anwendung als ¹single-source-Precursorenª in der CVD-Technologie [4±8]. Wie bereits fru È here Untersuchungen an Aminoalanen [(R 2 N) n AlH 3±n ] be-legen, liegen diese Verbindungen nicht monomer vor, sondern treten unter Bildung von l-Aminogruppen zu cyclischen Dimeren oder Trimeren mit AlN-Geru È st zusammen [9].…”

Section: Introductionunclassified

Si-O-Bindungsspaltung in einem Siloxamin durch Aluminiumhydrid

Veith

Spaniol

1998

Z. anorg. allg. Chem.

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Setzt man das Alkoxyaminosilan tBu‐O[tBuN(H)]SiMe2 (1) mit Aluminiumhydrid um, so isoliert man nicht das erwartete cyclische Alkoxyaluminosiloxan tBuO(tBuN)(AlH2)SiMe2 (2). Statt dessen reagiert 1 mit zwei Äquivalenten Aluminiumhydrid zum Alkoxyaminodialan 3, (tBuO)(AlH2)[N(SiMe2H)tBu](AlH2). Die Verbindung 3 kann über spektroskopische Methoden und über eine Einkristallröntgenstrukturanalyse zweifelsfrei charakterisiert werden: sie besteht aus einem OAl2N‐Vierring (Al–O 1.817(2) Å, Al–N 1.970(1) Å), wobei am Sauerstoff‐ und Stickstoffatom eine tert‐Butyl bzw. tert‐Butyl und eine HMe2Si‐Gruppe gebunden sind, während die Aluminiumatome nur Wasserstoffatome als Liganden besitzen. Die Si–O Bindung im Ausgangsmolekül 1 ist also gespalten worden, wobei die Sauerstoffvalenz durch Aluminium und die Siliciumvalenz durch Hydrid abgesättigt wird.

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Functional group reductions with Lewis base adducts of gallane

Cited by 38 publications

References 14 publications

Gallium Hydrides and O/N‐Donors as Tunable Systems in C−F Bond Activation

Gallium Hydrides and O/N‐Donors as Tunable Systems in C−F Bond Activation

Some Synthetic Uses of Double‐Bonded Functional Groups

Si-O-Bindungsspaltung in einem Siloxamin durch Aluminiumhydrid

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