An Efficient Method for Conversion of Carboxylic Acid Derivatives to Allylsilanes¹

References

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• Marks , T. J. and Fragala , I. L. 1985 . “ Fundamental and Technological Aspects of Organo-f-element Chemistry ” . Dordrecht , , Holland : D. Reidel Pub. Co. . Recent observations in our laboratory have shown that the stoichiometric ratio of anhydrous cerium(III)chloride to the organolithium reagent 9b can be altered from 1:1 (prepared and used at -78° C) to 1:2 (prepared and used at 0° C) with equal success with 3B (X=C1). For more information on trimethylsilylmethyl lanthanides, PO BOX 17,3300 AA
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• The suspension appears to thicken upon stirring and was well suspended without adhesion to the glassware and without aggregation after 12 hours. This “aging” of the anhydrous cerium(III) chloride/THF suspension was necessary in obtaining consistent results. See reference 10.
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• Reagents exhibiting other than a bright yellow color were found to be ineffective.
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• The Grignard reagent 9a showed no reaction with the esters or the acid chlorides at -78° C after 1 h. Warming to 0° C showed little change after 1 h. The reaction contents were then stirred at room temperature for 3 days, quenched with TMSCl and worked up as described.
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• Ruden , R. and Gaffney. , B. L. 1975 . Syn. Comm. , 5 : 15 The lithium reagent 9b is available from Aldrich (1.0M in pentane), or Also see reference 9a. Reference to crystalline form: Connolly, J.W., Urry, G. Inorg. Chem., 1963, 2, 645; Burford, C., Cooke, F., Roy, G., Magnus, P. Tetrahedron, 1983, 39, 867.
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• Use of less than 6 mol equivalents of the acid-free TMSCI was not satisfactory
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• The acid-free TMSC1 was prepared by the method of Hutchinson, D.K., Aidrichimica Acta, submitted. The method involves distillation of the TMSCI under an argon atmosphere from calcium hydride, transfer under argon to a bottle fitted with a vycor or teflon stopper containing 1/8 dry volume of crosslinked poly(4-vinyIpyridine). The contents are then shaken and allowed to stand at room temperature 2-3 days prior to use.
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• The allylic silanes showed decomposition by TLC if left in pentane for more than 3 to 6 hours at room temperature (the dienylic silanes were especially labile in CDC13). Generally, the allylic silanes were observed to be stable at 0° C.
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