Total Synthesis Guided Structure Elucidation of (+)‐Psychotetramine

Solving the puzzles: Total synthesis played a key role in the elucidation of the stereochemistry and verification of the constitution of the complex polymeric natural product psychotetramine. The route features three powerful assembly processes that enabled four rounds of total synthesis-guided structure determination. The pursuit of this alkaloid also led to an improved procedure for indole–aniline coupling and a highly efficient enantioselective synthesis of psychotrimine. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.