First Total Synthesis of (±)‐13‐Hydroxyneocembrene

First total synthesis of (±)‐13‐hydroxyneocembrene ( 1 ), starting from 6‐methyl‐5‐hepten‐2‐one ( 6 ) and geraniol ( 7 ), is described. The key steps are (i) the addition of sulfur‐stabilized carbanion 12 to aldehyde 9 , (ii) the synthesis of 18 by using phase‐transfer catalyzed coupling reaction, and (iii) low‐valent titanium‐induced intramolecular coupling of oxo aldehyde 3 to afford the target molecule after the final deprotection.