Preparation of partially substituted 1-halo- and 1,4-dihalo-1,3-dienes via reagent-controlled desilylation of halogenated 1,3-dienes.
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-trimethylsilyl-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(trimethylsilyl)-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.
Xi
Zhenfeng
Z
Bejing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China. zfxi@pku.edu.cn
Song
Zhiyi
Z
Liu
Guangzhen
G
Liu
Xiaozhong
X
Takahashi
Tamotsu
T
D006219:Halogens / Q000737:chemistry*; D008745:Methylation; D015394:Molecular Structure; D013237:Stereoisomerism
D006219:Halogens