- Eosin-Mediated Alkylsulfonyl Cyanation of Olefins
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Eosin-Y (EY)-mediated alkylsulfonyl cyanation of olefins was shown to afford alkylsulfonyl nitriles in good yields. On the basis of transient absorption spectroscopy, the reaction was shown to proceed via photoinduced electron transfer from 3EY? to an O-cyanated derivative of the photocatalyst, formed in situ, with generation of the corresponding sulfinate that is oxidized by EY?.+ into a sulfonyl radical. Addition of the latter on the olefin, followed by a radical cyano group transfer, then furnished the nitrile along with a RSO2 radical sustaining the radical chain.
- Pirenne, Vincent,Kurtay, Gülbin,Voci, Silvia,Bouffier, Laurent,Sojic, Neso,Robert, Frédéric,Bassani, Dario M.,Landais, Yannick
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supporting information
p. 4521 - 4525
(2018/08/09)
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- Free-Radical Carbocyanation of Olefins
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The free-radical three-component carbocyanation of electron-rich olefins was investigated with p-tosyl cyanide as cyanide source. The scope and limitations of the process were established by varying the nature of the alkene and radical precursor. Carbocyanation of chiral allylsilanes was shown to occur with high diastereocontrol, leading to syn β-silyl nitriles. The origin of the stereocontrol was rationalized by a Felkin–Anh-type transition-state model. Finally, a tin-free carbocyanation process was also devised, based on the use of a new alkylsulfonyl cyanide incorporating both carbon fragments to be added across the olefinic π system.
- Hassan, Haitham,Pirenne, Vincent,Wissing, Maren,Khiar, Chahinaz,Hussain, Ashique,Robert, Frédéric,Landais, Yannick
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supporting information
p. 4651 - 4658
(2017/04/13)
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