An Efficient Synthesis of (±)-Dehaloperophoramidine.

Perophoramidine and communesin F are structurally related indole alkaloids with an intriguing polycyclic core containing vicinal all-carbon quaternary stereocenters. Dehaloperophoramidine is a dehalogenated synthetic analogue of perophoramidine. Synthetic studies toward the total synthesis of dehaloperophoramidine have led to the discovery of two novel domino processes, the first encompassing four steps and resulting in the formation of an ortho-amide. A thorough study of the reactivity of the ortho-amide functionality revealed the second domino reaction and ultimately yielded the target molecule. The vicinal all-carbon quaternary stereocenters having trans relative stereochemistry are constructed early in the reaction sequence by employing Overman's samarium mediated reductive dialkylation procedure. Described are the synthetic studies that led to the final eight-step synthesis of dehaloperophoramidine.

Concise Total Synthesis of Dehaloperophoramidine.

Perophoramidine, dehaloperophoramidine, and communesin F are structurally related alkaloids having intriguing polycyclic structures. A strategy for the synthesis of dehaloperophoramidine has been developed. In this synthesis all skeletal atoms and all functional groups required to reach the target molecule are incorporated early in the sequence. This approach led to the discovery of two novel substrate-specific domino processes, one encompassing four steps and the other comprising five steps, thus resulting in an eight-step synthesis of dehaloperophoramidine.