Scalable Total Synthesis of <i>rac</i>‐Jungermannenones B and C

Abstract

Reported is the first scalable synthesis of rac-jungermannenones B and C starting from the commercially available and inexpensive geraniol in 10 and 9 steps, respectively. The unique jungermannenone framework is rapidly assembled by an unprecedented regioselective 1,6-dienyne reductive cyclization reaction which proceeds through a vinyl radical cyclization/allylic radical isomerization mechanism. DFT calculations explain the high regioselectivity observed in the 1,6-dienyne reductive radical cyclization.