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Synthesis of New Cyclic Homoconjugated Oligodiacetylenes
Author(s) -
Leibrock Bernd,
Vostrowsky Otto,
Hirsch Andreas
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200112)2001:23<4401::aid-ejoc4401>3.0.co;2-p
Subject(s) - synthon , chemistry , acetylene , ring (chemistry) , stereochemistry , coupling reaction , polymer chemistry , medicinal chemistry , crystallography , organic chemistry , catalysis
Cyclic homoconjugated oligodiacetylenes, consisting of butadiyne subunits interconnected with two different sp 3 ‐linkers in alternation, were synthesized by coupling of different 1,4‐pentadiyne synthons. The “exploded” [4]pericyclyne 7 was obtained in a “one‐pot” random cyclodehydro‐oligomerization reaction, by cross‐coupling of two different 1,4‐pentadiyne units. Larger ring structures such as the C 30 macrocyclic [6]pericyclyne 22 and the unsymmetrically diyne‐tetrayne expanded C 24 ‐[4]pericyclyne 27 afforded a stepwise approach. Heterocoupling of two different 1,4‐pentadiynes in a molecular ratio of 1:2 and 2:1 afforded the symmetrical pentadecahexaynes 12 and 20 , respectively. Cyclodehydro‐dimerization gave the symmetrically patterned cyclotriacontadodecayne 22 . A collective heterocoupling of two different 1,4‐pentadiynes with TIPS‐acetylene resulted in the formation of acyclic dodecapentayne 26 . Final cyclodimerization yielded the cyclotetracosadecayne 27 .