α-Silyl Ethers as Hydroxymethyl Anion Equivalents in Photoinduced Radical Electron Transfer Additions

Guido Gutenberger; Eberhard Steckhan; Siegfried Blechert

doi:10.1002/(SICI)1521-3773(19980316)37:5<660::AID-ANIE660>3.0.CO;2-8

α-Silyl Ethers as Hydroxymethyl Anion Equivalents in Photoinduced Radical Electron Transfer Additions

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.

Authors

Guido Gutenberger¹, Eberhard Steckhan¹, Siegfried Blechert²

Affiliations

¹ Kekulé Institut für Organische Chemie und Biochemie der Universität, Gerhard-Domagk-Strasse 1, D-53121 Bonn (Germany), Fax: (+49) 228-735683.
² Institut für Organische Chemie der Technischen Universität Berlin.

PMID: 29711086
DOI: 10.1002/(SICI)1521-3773(19980316)37:5<660::AID-ANIE660>3.0.CO;2-8

Abstract

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=PhCH₂ , tBuMe₂ Si, Me; TMS=Me₃ Si.

Keywords: Electron transfer; Photochemistry; Radical ions; Silicon.