Trimethylsilylmethylmagnesium chloride

Related Reagents. Bis(trimethylsilyl)methane (diisopro-poxymethylsilyl)methylmagnesium chloride trimethylsilyl-methylmagnesium chloride (trimethylstannylmethyl)lithiunL 

Martinez, C. DeLos Santos, J., Tetrahedron Lett. 2000,47, 

A list of General Abbreviations appears on the front Endpapers 

Solubility sol ethereal solvents reacts with protic solvents. Preparative Method from (chloromethyl)trimethylsilane and magnesium in an ethereal solvent.  

Handling, Storage, and Precautions this Grignard reagent reacts with protic solvents. 

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The NiCl2py4 complex reacts with trimethylsilylmethylmagnesium chloride in the presence of an excess of pyridine forming the air-unstable square planar complex [Ni(Me3SiCH2)2py2] from which the pyridine molecules are displaced by phosphines, 2,2 -bipyridyl, 1,10-phenanthroline and N,N,N, N -tetramethylethylenediamine.803... 

Trimethylsilylmethylmagnesium chloride Magnesium, [chloro[(trimethylsilyl)methyl -(8,9) (13170-43-9)... 

There is much current interest in the design and development of the "double functional group transformation" concept, an excellent illustration of which is the now well known and widely exploited Eschenmoser fragmentation reaction. A recent example of the "double functional group transformation" is the one-flask conversion of 1-nitrocycloalkenes into terminally unsaturated nitriles by treatment first with trimethylsilylmethylmagnesium chloride (1.8 eq.) in THF at -20°C and then, in situ, with PCI3 (2.5 eq.) at 67°C. 2-Nitrobicyclo[2.2.1]hept-2-ene, for example, gave cis-1 -cyano-3-vinylcyclopentane in 33% yield, and similar yields of ene-nitriles were obtained from a variety of monocyclic and bicyclic 1-nitrocycloalkenes. 

Trimethylsilyl)methylallyl iodide, 579 2-Trimethylsilylmethyl-1,3-butadiene, 580 Trimethylsilylmethyllithium, 581 Trimethylsilylmethylmagnesium chloride, 58,... 

Prepared in 70% yield by adding a solution of cyclohexylcarboxylic acid chloride (71.1 mmol) in THF to a solution of trimethylsilylmethylmagnesium chloride (72 mmol) and Cul (35.6 mmol) in THF at -40°C, followed by a standard extractive work-up, and distillation under reduced pressure. Colourless liquid, b.p. = 82-86°C (1.5 torr). 

Trimethylsilylmethylmagnesium chloride Magnesium, [chk>ro[(trimethylsilyl)-methyl)- (13170-43-9), 69, 89 3-Trimethylsilyl-2-propyn-1-ol, 66,1, 3 3-Trimethylsilyl-2-propyn-1-yl methanesulfonate, 66, 2... 

The reaction presumably goes through the addition of a radical (formed from RX) to the diene, followed by the reaction of the formed allyl radical with [NiU2Ar] complex. A combination of CoCl2 and l,6-bis(diphenylphos-phino)hexane catalyzes a similar reaction of an alkyl bromide with a 1,3-diene and trimethylsilylmethylmagnesium chloride, yielding homoallylic silanes in good to excellent yields.212 For both cases, the same catalytic cycle was proposed (Scheme 67). 

The nickel- or palladium-catalyzed reaction of stereodefined alkenyl halides with trimethylsilylmethylmagnesium chloride (TMSCH2MgCl) delivers allylsilanes with excellent regio- and stereocontrol. 

Hetero-Diels-Alder reaction. 3,4-Bis(trimethylsilyl)-5,6-dihydro-2A/-pyrans are accessible from a catalyzed cycloaddition under very mild conditions. The diene is prepared in 44-47% yield from the reaction of l,4-ditosyloxy-2-butyne with trimethylsilylmethylmagnesium chloride. 

Preparative Methods prepared by the diazo-transfer reaction of Trimethylsilylmethylmagnesium Chloride with Diphenyl Phosphorazidate (DPPA) (eq 1). ... 

It is readily converted to trimethylsilylmethylmagnesium chloride (see [13170-43-9] above) in —90% yield. It reacts with n-BuLi in pentane to give trimethylsilylmethylLi [Sommer et al. J Am Chem Soc 71 2750 1949, which reacts with anhydrous cerium (III) chloride to form trimethylsilylmethyl cerium dichloride. The latter reacts with acyl hahdes to provide bis-p-silylethyl tertiary alcohols that effidently undergo a trimethylchlorosilane-promoted Peterson reaction to generate allylsilanes in high overall yields [Anderson Fuchs Synth Commun 17 621 7987]. It is useful also for Peterson olefination and homologation of aldehydes and ketones via 1,2-epoxysilanes [Lee et al. Tetrahedron 45 5877 7989]. Trimethylsilylmethyl bromide [18243-41-9] has M 167.1, b 115.5 /atm, 1.17, Up 1.444 [Beilstein 4 IV 3878], and trimethylsilylmethyl iodide [4206-67-1] has M 214.1, h 139-141 /atm, df 1.433, ng 1.491 [Beilstein 4 IV 3878], and both should be stored in the dark. 

Preparative Method the best procedure for the preparation of trimethylsilylacetone is the reaction of trimethylsilyl-methylmagnesium chloride or bromide with acetic anhydride. Other useful preparative methods for a-trimethylsilyl ketones involve the reaction of trimethylsilylmethylmagnesium chloride with acid chlorides, or with aldehydes followed by oxidation of the resulting /3-hydroxysilane to the ketone. When the trialkylsilyl group is very large, particularly the triisopropylsilyl group, a rearrangement from the silyl enol ether to the a-silyl ketone is possible. ... 

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