Details

Autor(en) / Beteiligte

• Paulisch, Tiffany O
• Strieth-Kalthoff, Felix
• Henkel, Christian
• Pitzer, Lena
• Guldi, Dirk M
• Glorius, Frank

Titel

Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C-O vs. C-C double bonds

Ist Teil von

• Chemical science (Cambridge), 2020-01, Vol.11 (3), p.731-736

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Free E-Journal (出版社公開部分のみ）

Beschreibungen/Notizen

• Investigations into the selectivity of intermolecular alkyl radical additions to C-O- C-C-double bonds in α,β-unsaturated carbonyl compounds are described. Therefore, a photoredox-initiated radical chain reaction is explored, where the activation of the carbonyl-group through an generated Lewis acid - originating from the substrate - enables the formation of either C-O or the C-C-addition products. α,β-Unsaturated aldehydes form selectively 1,2-, while esters and ketones form the corresponding 1,4-addition products exclusively. Computational studies lead to reason that this chemo- and regioselectivity is determined by the consecutive step, an electron transfer, after reversible radical addition, which eventually propagates the radical chain.