The Hydroboration of 3-Chloro-1-iodo-1-propyne with Dialkylboranes, and Its Application to the Syntheses of Some Geminally Dialkylated Propene Derivatives
作者:Yuzuru Masuda、Masayuki Hoshi、Akira Arase
DOI:10.1246/bcsj.65.3294
日期:1992.12
dialkylboranes, giving (Z)-(3-chloro-1-iodo-1-propenyl)dialkylboranes exclusively. Subsequent treatment of the hydroboration mixture with sodium methoxide or aqueous sodium hydroxide results in migration of two alkyl groups from the boron atom to the α-alkenyl carbon atom to provide dialkylated allylboranes, which are protonolyzed with methanol or water to produce 1,1-dialkyl-1-propenes. Oxidation of
3-Chloro-1-iodo-1-propyne 与二烷基硼烷顺利进行硼氢化反应,仅生成 (Z)-(3-chloro-1-iodo-1-propenyl) 二烷基硼烷。随后用甲醇钠或氢氧化钠水溶液处理硼氢化混合物,导致两个烷基从硼原子迁移到 α-烯基碳原子,得到二烷基化烯丙基硼烷,用甲醇或水质子化生成 1,1-二烷基-1-丙烯。在质子分解之前用碱性过氧化氢氧化烯丙基硼烷得到 1,1-二烷基-2-丙烯-1-醇。用格氏试剂处理(Z)-(3-氯-1-碘-1-丙烯基)二环己基硼烷,然后用乙酸进行质子分解,得到 3-烷基-3-环己基-1-丙烯,其中衍生出烷基来自格氏试剂。