Total syntheses of (±)-21-oxogelsemine (
3) and(±)-gelsemine (
1) are described. Free radicalcyclizationsplay important roles in constructing the tricyclic core (
40
41) and oxindole (
93
96)substructures of the targetalkaloids, and an isomerization-cyclization strategy (
101
102) was used to complete construction of thegelseminecage. Observations made along the way include intramolecular 1,4-and 1,6-hydrogen atom transfers (
64
65and
40
47) and a free radicalcyclization-fragmentation sequence (
85
86 +
87). A retroaldol-aldol strategy foradjusting oxindole stereochemistry in gelsemine-like structures is alsodescribed (
72
74 and
86
87).