An efficient synthesis of ergot alkaloid lysergol and its analogues is described, providing compounds for functional evaluation at the human 5-HT, 5-HT, 5-HT, or 5-HT receptors. Key features of the synthesis include the development of a tandem reaction to construct the multifunctionalized piperidine skeleton and use of a rhodium-catalyzed [3 + 2] annulation in the late-stage indole formation.

A new and general method to functionalize the C(sp 3 )−C(sp 2 ) bond of alkyl and alkene linkages has been developed, leading to the dealkenylative generation of carbon-centered radicals that can be intercepted to undergo Ni-catalyzed C(sp 3 )−C(sp 2 ) cross-coupling. This one-pot protocol leverages the easily procured alkene feedstocks for organic synthesis with excellent functional group compatibility without the need for a photoredox catalyst.