A Convenient Preparation of Pure Dialkylmagnesium from a Grignard Reagent

Saheki, Yukitami; Sasada, Katsuhiko; Satoh, Nobumasa; Kawaichi, N.; Negoro, Kenji

doi:10.1246/cl.1987.2299

Cited by 24 publications

(12 citation statements)

References 4 publications

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“…All solvents were stored in a glovebox. Compound MCM-41 (M1), [18] 1, [16] 2 [16] 3, [17c] and MgMe 2 [43] were synthesized according to literature procedures. TEA was purchased from ABCR and used as received.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Surface Organobarium and Organomagnesium Chemistry on Periodic Mesoporous Silica MCM‐41: Convergent and Sequential Approaches Traced by Molecular Models

Michel

König

Törnroos

et al. 2011

Chemistry A European J

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The alkaline earth metal alkyl complexes [Ba(AlEt(4))(2)](n) and Mg(AlMe(4))(2) were directly grafted onto periodic mesoporous silica MCM-41, which had been dehydroxylated at 270 °C (specific surface area a(s): 1023 m(2) g(-1); pore volume V(p): 1.08 cm(3) g(-1); main pore diameter 3.4 nm). Alternatively, barium alkyl surface species were generated by sequential grafting of MCM-41 with Ba[N(SiHMe(2))(2)](2)(thf)(4) and AlEt(3) to yield the hybrid material AlEt(3)@Ba[N(SiHMe(2))(2)](2)(thf)(4)@MCM-41. For a better understanding of the surface chemistry, AlEt(3)@MCM-41 was also accessed. All hybrid materials were analyzed by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, elemental analysis, nitrogen physisorption, and solid-state NMR spectroscopy; this clearly revealed distinct surface chemistry for the alkylaluminate-treated materials [Ba(AlEt(4))(2)]@MCM-41 and Mg(AlMe(4))(2)@MCM-41. In an attempt to mimic the surface chemistry, the organometallic precursors were treated with HOSi(OtBu)(3). The reaction of equimolar amounts of {Ba[N(SiHMe(2))(2)](2)}(n) and HOSi(OtBu)(3) produced a mixed silylamido/siloxide cluster of Ba(3)[OSi(OtBu)(3)](3)[N(SiHMe(2))(2)](3) with bridging-only siloxide ligands as well as one bridging and two terminal silylamido ligands. The Schlenk equilibrium was found to govern the [Ba(AlEt(4))(2)](n)-HOSi(OtBu)(3) and Mg(AlMe(4))(2)-HOSi(OtBu)(3) reactions, leading to the isolation of complexes of [Ba(AlEt(4))(2) (toluene)](2) and Mg[OSi(OtBu)(3))](2)(AlMe(3))(2), respectively. Allowing for a donor-induced cleavage of Mg(AlMe(4))(2), the reaction of [MgMe(2)] with one or two equivalents of HOSi(OtBu)(3) was studied. While putative Mg[OSi(OtBu)(3)](Me) and Mg[OSi(OtBu)(3)](2) could not be crystallized from the reaction mixtures, cluster complexes Mg(5)(O)[OSi(OtBu)(3)](5)Me(3) and Mg(4)(OH)(2)[OSi(OtBu)(3)](6) could be unambiguously identified by X-ray crystallography.

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Section: Wwwchemeurjorgmentioning

confidence: 99%

Surface Organobarium and Organomagnesium Chemistry on Periodic Mesoporous Silica MCM‐41: Convergent and Sequential Approaches Traced by Molecular Models

Michel

König

Törnroos

et al. 2011

Chemistry A European J

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“…Although we expected the intended bromine-magnesium exchange to proceed relatively fast, [21] exposing 8 a in THF solution to essentially the same conditions as 5, [22] that is to slight excesses both of MgHal 2 -free iPr 2 Mg [23] and the lithium salt (Li-11) of the monomethyl ether (11) [24] of (S)-BINOL (À40 8C, 20 min) we obtained none of the expected diaryl sulfoxide 7 a but 25 % isopropyl phenyl sulfoxide (+)-(R)-9 b and 57 % bromoisopropyl phenyl sulfoxide (+)-(R)-9 a (Scheme 1, middle). This suggested that a selective sulfoxide-magnesium exchange [25] had occurred first (!…”

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confidence: 99%

“…[b] Conditions: 11 (1.5 equiv), THF, nBuLi (1.5 equiv), 0 8C, 10 min; 22 8C, 10 min; iPr 2 Mg [23] (1. symmetrizes dibromo sulfoxide 8 a as well (! 7 a + iPrBr).…”

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Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Hampel

Ruppenthal

Sälinger

et al. 2012

Chemistry A European J

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Transparent glass‐ceramics containing Ln3+‐doped YF3 nanocrystals are successfully obtained under adequate thermal treatment of precursor sol–gel glasses for the first time, to the best of our knowledge. Precipitation of YF3 nanocrystals is confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy images. An exhaustive structural analysis is carried out using Eu3+ and Sm3+ as probe ions of the final local environment in the nano‐structured glass–ceramic. Noticeable changes in luminescence spectra, related to relative intensity and Stark structure of band components, along with remarkably different lifetime values, allow us to discern between ions residing in precipitated YF3 nanocrystals and those remaining in a glassy environment. A large fraction of optically active ions is efficiently partitioned into nanocrystals of small size, around 11 nm. Moreover, bright and efficient up‐conversion, including very intense high‐energy emissions in the UV range, due to 4‐ and 5‐infrared photon processes, are achieved in Yb3+–Tm3+ co‐doped samples. Up‐conversion mechanisms are analysed in depth by means of intensity dependence on sensitiser Yb3+ concentration and pump power.

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“…All materials were purchased from Aldrich chemical company, Acros Organics, or Fisher Scientific, with the exception of dimethylmagnesium and diethylmagnesium, which were prepared by the method of Saheki et al [24]. Diethyl ether was dried by distillation under N 2 from sodium/benzophenone ketyl.…”

Section: Methodsmentioning

confidence: 99%

Zirconocene catalysis in the synthesis of 1,4-dimagnesium reagents: using competitive inhibition to suppress β-hydrogen abstraction

Fielding

Gao

Knight

2010

Transition Met Chem

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Substituted 1,4-dimagnesium reagents were synthesized by the zirconocene-catalyzed reaction of alkenes with ethylmagnesium reagents in the presence of a methylmagnesium containing additive. Improved selectivity for formation of dimagnesium reagents over monomagnesium reagents was obtained in the presence of the methylmagnesium containing additive. The ratio of monoto dimagnesiated products was extrapolated from the ratio of alkene to diene in the products formed when the reaction was quenched with allyl bromide. The extent of the increase in the alkene/diene ratio was dependent on the type of organomagnesium halide, with greatest increases (59%) for the alkylmagnesium chlorides. A mechanism for improved selectivity by suppression of b-hydrogen abstraction in the catalytic cycle is presented. Quenching the 1,4-dimagnesium reagents with allyl bromide yielded decadienes.

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A Convenient Preparation of Pure Dialkylmagnesium from a Grignard Reagent

Cited by 24 publications

References 4 publications

Surface Organobarium and Organomagnesium Chemistry on Periodic Mesoporous Silica MCM‐41: Convergent and Sequential Approaches Traced by Molecular Models

Surface Organobarium and Organomagnesium Chemistry on Periodic Mesoporous Silica MCM‐41: Convergent and Sequential Approaches Traced by Molecular Models

Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Zirconocene catalysis in the synthesis of 1,4-dimagnesium reagents: using competitive inhibition to suppress β-hydrogen abstraction

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