Straightforward Synthesis of 2‐ and 2,8‐Substituted Tetracenes

A simple regiospecific route to otherwise problematic substituted tetracenes is described. The diverse cores (E)‐1,2‐Ar1CH2(HOCH2)C=C(CH2OH)I (Ar1=Ph, 4‐MePh, 4‐MeOPh, 4‐FPh) and (E)‐1,2‐I(HOCH2)C=C(CH2OH)I, accessed from ultra‐low cost HOCH2C≡CCH2OH at multi‐gram scales, allow the synthesis of diol libraries (E)‐1,2‐Ar1CH2(HOCH2)C=C(CH2OH)CH2Ar2 (Ar2=Ph, 4‐MePh, 4‐iPrPh, 4‐MeOPh, 4‐FPh, 4‐BrPh, 4‐biphenyl, 4‐styryl; 14 examples) by efficient Negishi coupling. Copper‐catalysed aerobic oxidation cleanly provides dialdehydes (E)‐1,2‐Ar1CH2(CHO)C=C(CHO)CH2Ar2, which in many cases undergo titanium(IV) chloride‐induced double Bradsher closure, providing a convenient method for the synthesis of regiochemically and analytically pure tetracenes (12 examples). The sequence is typically chromatography‐free, scalable, efficient and technically simple to carry out. Tetracene and not hard: A procedure is reported for the preparation of substituted tetracenes from low‐cost ArCH2Cl and HOCH2C≡CCH2OH. The sequence is typically chromatography‐free, scalable, efficient and technically simple to carry out.