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Please login to access the full content or check if you have access via4.4.40.30 Method 30: From Carboxylic Acid Derivatives and an Organocerium Reagent by a Peterson-type Reaction
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Sarkar, T. K., Science of Synthesis, (2002) 4, 874.
2-Substituted allylsilanes have been prepared from carboxylic acid derivatives such as esters by exposure to a twofold excess of organocerium reagent, prepared in situ from [(trimethylsilyl)methyl]magnesium chloride and cerium(III) chloride, followed by a Peterson-type elimination of the resultant bis(silylmethyl)carbinols. This method has, for example, been used in the formation of silane 116 (Scheme 51).[181] Chiral 2-substituted allylsilanes, for example, 117,[182] as well as allylsilanes containing acid-sensitive functional groups, for example, 118[183,184] are also available by this method (Scheme 51). This procedure is equally applicable to lactones as substrates, as shown by the preparation of silane 119.[183,185] The trick for successful preparation of allylsilanes by this method is to use a good-quality Grignard reagent and anhydrous reaction conditions.[181,185] However, sterically highly congested esters, such as adamantane-1-carboxylate do not react under these conditions.[181] An analogous procedure using an organocerium reagent derivable in situ from [(trimethylsilyl)methyl]lithium and cerium(III) chloride has limited scope, and is suitable only for acid chlorides.[186]
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Meeeeeeeeeee Meeeeeeee
(8-Meeeeeeeeeeeeee)eeeeeeeeeeeeeee (888); Meeeeee Meeeeeeee:[888]
Meeeeeee MeMe8•8M8M (8.88 e, 8.8 eeee) eee eeeee ee 888°M/8.8 Meee eee 8 e. Mee eeeee eee eeeeee ee ee, eee eeeeee ee e eee M8 eeeeeeeeee. Mee MMM (88 eM) eee eeeee, eee eee eeeeeeeeee eee eeeeeee ee ee eeeee M8 eee 8 e. Mee eeeeee eee eeee eeeeee ee −88°M, eee 8 M Me8MeMM8MeMe ee Me8M (8 eM, 8 eeee) eee eeeee ee eeeeeee. Mee eeeee-eeeeeee eeeeeeeeee eee eeeeeee ee −88°M eee 8 e, eee eeee eeeeee eeeeeeeeeeeeeeeeeeeeee (888 ee, 8 eeee) eee eeeee eeee 8–8 eee. Meeeeeee eee eeeeeeeee eee 8 e ee −88°M, eee eeee eee eeeeeee eee eeeeeee ee eeee ee ee eeeeeeeee. Meeee eee eeeeeeee eee eeee eeeeeeee eeee 8 M MMe (88 eM), eee eeeee α-eee[(eeeeeeeeeeeeee)eeeeee] eeeeeee eee eeeeeeee ee eeeeeeeeee eeee MM8Me8, eeeee (MeMM8), eee eeeeeeeeeeee ee eeeee. Mee eeeeeee eee eeeeeeeeeeeeeeeeee ee eeeee eeeeeee eeee eeeeee-eeeeeeeeeeeeee-eeeee eeeeee eee (8 e) eee MM8Me8 (88 eM) eee 8–8 e. Meeeeeeeee, eeeeeeee ee eeeee eeeeeeeeeeeeee eeeeeeee eeeeeeeeeee 888; eeeee: 888 ee (88%).
References
[181] | Meeeeeeee, M. M.; Meeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[182] | Meeeee, M.; Meeee-Meeeee, M.; Meeeeee, M. -M.; Meeeeee, M., Meeeeeeeeee: Meeeeeeee, (8888) 8, 8888. |
[183] | Mee, M. M.; Meeeee, M. M.; Meeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[184] | Meeeeee, M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[185] | Mee, M. M.; Meeeeee, M. M.; Meeee, M.; Meeeee, M. M.; Meeee, M. M.; Meee, M. M.-M., Meeeeeeeeee, (8888) 88, 8888. |
[186] | Meeeeeee, M. M.; Meeee, M. M., Meeee. Meeeee., (8888) 88, 888. |
[187] | Meeeee, M. M.; Meeeeeeeeee, M. M.; Meeeeee, M. M., Meee. Meee. Meee MMMM, (8888) 888, 88; Meee. Meee. (Meee. Meeeee.), (8888), 88. |
[188] | Meeeeee, M.; Meeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[189] | Meeeeeee, M.; Meeeeeee, M., Meee. Meee., (8888), 888. |
[190] | Meeeee, M., Meeeeeeee, (8888), 888. |
[191] | Meeeee, M.; Meeeee, M.; Meeeeee, M.; Meeeeeeee, M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[192] | ee Meeee, M.; Meeee, M. M., Meeeeeeee. Mee., (8888) 888, 888. |
[193] | Meeeeeee, M.; Meeeeeeee, M.; Meeeeeeee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[194] | Mee, M.-M.; Meee, M.-M.; Meeee, M.; Mee, M.-M., Meeeeeeeeee, (8888) 88, 8888. |