On Demand Synthesis of C3−N1' Bisindoles by a Formal Umpolung Strategy: First Total Synthesis of (±)‐Rivularin A.

In this work, a straightforward synthesis of C3−N1' bisindolines is achieved by a formal umpolung strategy. The protocols were tolerant of a wide variety of substituents on the indole and indoline ring. In addition, the C3−N1' bisindolines could be converted to C3−N1' indole‐indolines and C3−N1'‐bisindoles. Also, we have successfully synthesized (±)‐rivularin A through a biomimetic late‐stage tribromination as a key step. [ABSTRACT FROM AUTHOR]