Silicon-induced diastereoselectivity of the catalyzed phosphorylation of 1-(perfluoroalkyl)-ω (trialkylsilyl)alkan-1-ols
作者:G. N. Molchanova、T. M. Shcherbina、P. V. Petrovskii、I. Yu. Kudryavtsev、L. S. Zakharov
DOI:10.1007/s11172-005-0064-3
日期:2004.9
1-(perfluoroalkyl)-ω-(trialkylsilyl)alkan-1-ols with pentavalent phosphorus acid monochlorides (phosphonochloridates, methyl(phenyl)phosphinic chloride, and phosphorochloridates) was studied. The effects of the structures of alcohols and phosphorylating agents on the degree of the reaction diastereoselectivity were investigated. Methylphosphonochloridates were found to react most stereoselectively; the diastereoselectivity
研究了 1-(全氟烷基)-ω-(三烷基甲硅烷基)链烷-1-醇与五价磷酸一氯化物(膦酰氯、甲基(苯基)次膦酰氯和磷酰氯)催化磷酸化的立体化学。研究了醇和磷酸化剂的结构对反应非对映选择性程度的影响。发现甲基膦酰氯的反应立体选择性最强;磷酸化的非对映选择性与磷原子上取代基的供体或受体特征无关,由它们的体积决定。在甲硅烷醇系列中,反应的非对映选择性越高,Si原子越靠近分子的反应位点,全氟烷基取代基的体积越大,Si原子上的取代基的吸电子特性越明显。提出了一种反应机制,使反应的立体选择性合理化。