Photoredox-Catalyzed Stereoselective Radical Reactions to Synthesize Nucleoside Analogues with a C2′-Stereogenic All-Carbon Quaternary Center
2019
Becerril-Jiménez, Fabiola | Lussier, Tommy | Leblanc, Louis | Eymard, Carla | Dostie, Starr | Prévost, Michel | Guindon, Yvan
The design of novel nucleoside analogues bearing a C2′ all-carbon quaternary center is described. The construction of this all-carbon stereogenic center involves the use of photoredox catalysis to initiate an intramolecular attack of a silyl-tethered vinyl functionality on a tertiary radical. Density functional theory calculations were performed to explore the origin of the high syn diastereoselectivity obtained through the preferred 5-exo-trig cyclization mode. The intramolecular vinyl addition also enables the preparation of the complementary configuration of the C2′ all-carbon stereocenter when performed after lactonization.
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