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Straightforward Synthesis of 2‐ and 2,8‐Substituted Tetracenes
Author(s) -
Woodward Simon,
Ackermann Miriam,
Ahirwar Saurabh K.,
Burroughs Laurence,
Garrett Mary Robert,
Ritchie John,
Shine Jonathan,
Tyril Björk,
Simpson Kevin,
Woodward Peter
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701170
Subject(s) - chemistry , negishi coupling , diol , biphenyl , chloride , stereochemistry , combinatorial chemistry , medicinal chemistry , catalysis , organic chemistry
A simple regiospecific route to otherwise problematic substituted tetracenes is described. The diverse cores ( E )‐1,2‐Ar 1 CH 2 (HOCH 2 )C=C(CH 2 OH)I (Ar 1 =Ph, 4‐MePh, 4‐MeOPh, 4‐FPh) and ( E )‐1,2‐I(HOCH 2 )C=C(CH 2 OH)I, accessed from ultra‐low cost HOCH 2 C≡CCH 2 OH at multi‐gram scales, allow the synthesis of diol libraries ( E )‐1,2‐Ar 1 CH 2 (HOCH 2 )C=C(CH 2 OH)CH 2 Ar 2 (Ar 2 =Ph, 4‐MePh, 4‐ i PrPh, 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‐Ar 1 CH 2 (CHO)C=C(CHO)CH 2 Ar 2 , 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.