Polarity-Reversal-Catalyzed Hydrostannylation Reactions: Benzeneselenol-Mediated Homolytic Hydrostannylation of Electron-Rich Olefins
作者:Leigh Ford、Uta Wille、Carl H. Schiesser
DOI:10.1002/hlca.200690214
日期:2006.10
hydrostannylation reactions involving electron-rich olefins results in a dramatic improvement in yield. For example, reaction of α-[(tert-butyl)dimethylsilyl]oxy}styrene (1) with triphenylstannane (2a; 1.1 equiv.) in the presence of PhSeSePh and 2,2′-azobis[2-methylpropanenitrile] (AIBN) affords 2-[(tert-butyl)dimethylsilyl]oxy}-2-phenylethyl}triphenylstannane (3a) in 95% yield after 2 h. This reaction presumably
在涉及富电子烯烃的加氢苯乙烯基化反应中加入10摩尔%的二苯二硒化物可显着提高收率。例如,在PhSeSePh和2,2'-偶氮双[2-甲基丙烷]存在下,α -[(叔丁基)二甲基甲硅烷基]氧基}苯乙烯(1)与三苯基锡烷(2a ; 1.1当量)反应)在2小时后以95%的收率得到2-[(叔丁基)二甲基甲硅烷基]氧基} -2-苯基乙基}三苯基锡烷(3a)。据推测,该反应得益于原位产生的极性反转催化剂苯硒酚的H原子转移速率的提高。