α-硅基醚作为光诱导自由基电子转移加成反应中羟甲基阴离子等价物
α-Silyl Ethers as Hydroxymethyl Anion Equivalents in Photoinduced Radical Electron Transfer Additions.
作者信息
Gutenberger Guido, Steckhan Eberhard, Blechert Siegfried
机构信息
Kekulé Institut für Organische Chemie und Biochemie der Universität, Gerhard-Domagk-Strasse 1, D-53121 Bonn (Germany), Fax: (+49) 228-735683.
Institut für Organische Chemie der Technischen Universität Berlin.
出版信息
Angew Chem Int Ed Engl. 1998 Mar 16;37(5):660-662. doi: 10.1002/(SICI)1521-3773(19980316)37:5<660::AID-ANIE660>3.0.CO;2-8.
Nucleophilic α-hydroxymethyl radicals can be generated from α-silyl ethers by irradiation in the presence of 9,10-anthracenedicarbonitrile (ADC) and biphenyl (BP). Under these conditions the hydroxymethyl radicals are not oxidized further but add directly to electron-poor alkenes [Eq. (a); EWG=electron-withdrawing group]. The radical adduct undergoes back electron transfer to form the carbanion, which is protonated. R=PhCH , tBuMe Si, Me; TMS=Me Si.
亲核性α-羟甲基自由基可通过在9,10-蒽二腈（ADC）和联苯（BP）存在下照射α-硅醚产生。在这些条件下，羟甲基自由基不会进一步氧化，而是直接加成到缺电子烯烃上[式（a）；EWG=吸电子基团]。自由基加合物发生逆向电子转移形成碳负离子，然后碳负离子被质子化。R=PhCH₂、tBuMe₂Si、Me；TMS=Me₃Si。
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