Total Syntheses of Hosieines A–C

The collective total syntheses of (±)‐hosieines A–C with a cage‐like tetracyclic framework have been realized, which includes the first syntheses of hosieines B‐C. The key strategy of the synthesis employs a one‐pot domino reaction that involves Cu‐catalyzed [3+2] cycloaddition, 1,6‐enone formation, and 1,6‐aza‐Michael addition forming the 5/6/6‐aza‐tricyclic skeleton. Other salient synthetic tactics comprise a challenging double bond migration and a 1,4‐aza‐Michael addition reaction to afford the tetracyclic framework. The collective total syntheses of (±)‐hosieines A–C featuring a cage‐like tetracyclic framework have been realized. The key synthetic strategy features a one‐pot domino reaction that forms two bonds and three consecutive stereocenters to construct the desired 5/6/6‐aza tricyclic skeleton. Other salient synthetic tactics comprise a challenging double bond migration and a 1,4‐aza‐Michael addition reaction to afford the tetracyclic framework.