Preparation of partially substituted 1-halo- and 1,4-dihalo-1,3-dienes via reagent-controlled desilylation of halogenated 1,3-dienes

作者：Xi ZF; Song ZY; Liu GZ; Liu XZ; Takahashi T^*

来源：Journal of Organic Chemistry, 2006, 71(8): 3154-3158.

DOI：10.1021/jo060003f

Depending on the desilylation reagents used, 1-halo-1,4-bis(trimethylsilyl)-1,3-butadienes afforded either 1-halo-1-trimethylsilyl-1,3-butadienes or 1-halo-4-trimethylsilyi-1,3-butadienes in excellent yields with excellent selectivity, respectively, when treated with CF3COOH or with NaOMe. These monosilylated 1,3-butadiene products could be further desilylated to generate their corresponding halobutadienes via the above reagent-controlled desilylation reaction. When 1,4-dihalo-1,4-bis(trimethylsilyi)-1,3-dienes were treated with MeONa/MeOH at room temperature, desilylation of both of the two trimethylsilyl groups took place to afford their corresponding 1,4-dihalo-1,3-dienes in excellent yields. The commonly used desilylation reagent CF3COOH did not work for these dihalobutadienes.

• 出版日期2006-4-14
• 单位北京大学