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 silyltethered 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.