- Tertiary α-diarylmethylamines derived from diarylketimines and organomagnesium reagents
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Organomagnesium reagents enable swift and versatile derivatisation of diarylimines to the corresponding α-substituted diarylmethylamines in excellent yields, through fast and clean reactions. Where it occurs, 1,2-reduction can be circumvented using readily accessible dialkylmagnesium reagents. This journal is
- Desmarchelier, Alaric,Ortiz, Pablo,Harutyunyan, Syuzanna R.
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supporting information
p. 703 - 706
(2015/01/09)
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- Symmetric diarylsulfoxides as asymmetric sulfinylating reagents for dialkylmagnesium compounds
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At -78 °C, primary dialkylmagnesium compounds reacted with diarylsulfoxides when 1.5 equiv of the dilithium salt of (S)-BINOL was added as a promotor. Alkyl aryl sulfoxides resulted in up to quantitative yield and with up to 97% ee. This demonstrates the feasibility of asymmetric sulfinylations by achiral sulfinylating agents (from the perspective of Alkyl2Mg) as well as the feasibility of asymmetric sulfoxide-magnesium exchanges (from the perspective of Ar2SO).
- Ruppenthal, Simon,Brückner, Reinhard
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p. 897 - 910
(2015/01/30)
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- Method for producing alkyl-bridged ligand systems and transition metal compounds
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The invention relates to a method for producing highly substituted alkyl-bridged ligand systems on the basis of indene derivatives and transition metal compounds. Said alkyl-bridged ligand systems can be obtained in high yields using this method.
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- New Syntheses with Magnesium Hydride. Part 1: Hydromagnesiation of α-Olefins to Magnesium-dialkyls
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The addition of highly active magnesium hydride to α-olefins, hydromagnesiation, is a well known reaction.The use of cheap magnesium hydride exhibiting a lower reactivity is highly desirable for industrial purposes.In a combination of chemical and mechanical activation the low reactivity of high temperature magnesium hydride could be overcome thereby making a broad variety of magnesium alkyls accessible. Key words: Magnesium alkyls; hydromagnesiation; magnesium hydride.
- Knott, Wilfried,Klein, Klaus-Dieter
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p. 914 - 918
(2007/10/02)
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- Diorganomagnesium Compounds from Magnesium, Hydrogen, and 1-Alkenes and Their Application in Synthesis
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1-Alkenes are converted in high yields to the corresponding primary diorganomagnesium compounds by transition metal-catalyzed hydromagnesation reaction using catalytically prepared suspended (MgH2*) or dissolved magnesium hydride (MgH2').The most active hydromagnesation catalysts have been found to be combinations of zirconium tetrahalides with MgH2* or MgH2'.The reaction is highly regio- and chemoselective.The diorganomagnesium compounds prepared in situ from magnesium, hydrogen, and 1-alkenes can be applied to the synthesis of organic and organometallic compounds just as Grignard compounds (Scheme 3, reactions 3-11).Dioctylmagnesium undergoes the growth reaction with ethene in the presence of quinuclidine and is oxidized by molecular oxygen in high yield to 1-octanol. Key Words: Magnesium hydride, catalytically prepared / Hydromagnesation reactions / Magnesium, diorgano compounds, preparation from magnesium, hydrogen and 1-alkenes / Magnesium, diorgano compounds, application in syntheses / Magnesium, diorgano compounds, oxidation of
- Bogdanovic, Borislav,Bons, Peter,Konstantinovic, Stanimir,Schwickardi, Manfred,Westeppe, Uwe
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p. 1371 - 1384
(2007/10/02)
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- On the Lewis Acidity of Nickel(0), X. - Diorganylmagnesium Complexes of Nickel(0): (TMEDA)MgCH3(μ-CH3)Ni(C2H4)2
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Tris(ethene)nickel(0) reacts with dialkylmagnesium solvate complexes (n-Donor)MgR2 (R = CH3, C2H5, n-C3H7, C2H4CH=CH2, C6H5; n-Donor = Et2O, THF, dioxane, TMEDA) below -10 deg C to afford yellow crystaline, thermolabile compounds (n-Donor)MgR(μ-R)Ni(C2H4)2 (1-5).In addition, two equivalents of Ni(C2H4)3 react with (C4H8O2)Mg(C6H5)2 in ether to yield (Et2O)Mg(μ-C6H5)22 (6), in which a central diphenylmagnesium molecule is bound to two bis(ethene)nickel(0) groups.An X-ray structure analysis shows that (TMEDA)MgCH3(μ-CH3)Ni(C2H4)2 (1c) contains an almost planar bis(ethen)nickel(0)unit coordinated by a dimethylmagnesium solvate complex by a Mg-μ-CH3-Ni multiple center bond with a Ni-Mg interaction.According to their 1H- and 13C-NMR spectra, the bridging and terminal organyl groups of 1-3 do not exchange in solution at 0 deg C.Apparently the monophenyl derivatives 5a, b and the dinuclear complex 6 are in equilibrium with each other.
- Kaschube, Wilfried,Poerschke, Klaus-Richard,Angermund, Klaus,Krueger, Carl,Wilke, Guenther
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p. 1921 - 1930
(2007/10/02)
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- A Convenient Preparation of Pure Dialkylmagnesium from a Grignard Reagent
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Dimethyl ether of acyclic polyethers, Me(OCH2CH2)nOMe, preodominantly coordinated to MgX2 in an ether solution of Grignard reagent and the MgX2 adduct was removed as a precipitate.Consequently, an ethereal solution of pure R2Mg was obtained in reasonable yield.This method is more convenient than those known general.
- Saheki, Yukitami,Sasada, Katsuhiko,Satoh, Nobumasa,Kawaichi, Noriyuki,Negoro, Kenji
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p. 2299 - 2300
(2007/10/02)
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- Method of preparing di-organo-magnesium compounds
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A method of preparing a di-organo-magnesium compound of the formula R2 Mg in which R is an organic radical bonded to Mg by carbon, comprising reacting magnesium hydride MgH2 or magnesium and hydrogen with an olefin in the presence of a catalyst comprising a compound of a transition metal of the 4th to 8th secondary group and an organometallic compound or a hydride of a metal of the 1st to 3rd principal groups of the periodic system. Advantageously there is also present a polycyclic aromatic compound or a tertiary amine as activator and the reaction is effected in the presence of tetrahydrofuran as solvent at a pressure of about 1 to 300 bars at about 0° to 200° C., the atomic ratio of Mg:transition metal being from about 104 to 10:1, the molar ratio of transition metal compound:organometal compound or metal hydride being from about 0.1 to 10:1, the molar ratio of olefin:magnesium being from about 2 to 10:1 and the olefin being of the formula CH2 =CHR' wherein R' is H or an alkyl, cyclo-alkyl, aryl or aralkyl group.
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